Organometallic and Coordination Chemistry: Fundamental and Applied Aspects International Youth School-Conference on Organometallic and Coordination Chemistry

Wani  Aadil

Nanomaterials has become one of the most prominent subjects in diverse fields of applications. Nanomaterials have emerged as one of the most promising things in different fields ranging from biomedical to pharmaceutical. The word nanomaterial originated from the Latin word 'Nanos' which means very small. Hence nanomaterials are particles of extremely small dimensions in the range of nanoscale. Nanotechnology has just added to the number of creative items in different building disciplines due to their remarkable and compensating substance, physical, and mechanical properties. One famous utilization of nanomaterials is nanotubes. Carbon nanotubes (CNT) are one of an illuminative model for the capability of nanotechnology. The elasticity of high carbon steel is around 1.2 GPa however the rigidity of carbon nanotubes (CNT) is 63 GPa. Likewise they are known to be perhaps the most grounded material having been created by nanotechnology up until this point. 1.1) WHAT ARE NANOMATERIALS? Nanomaterials can be seen as the building blocks or cornerstones of nanotechnology. Nanomaterials are defined as substances having at least one dimension in nanoscale i.e. less than approximately 100 nanometers. These materials play an important role because of the presence of unique magnetic, electrical ,optical and many other such properties at such a small scale. Many properties are seen to emerge at nanoscale range. Hence , Nanomaterials deal with substances in the range of 1-100 nm. 1.2) HISTORY The history of Nanomaterials started all after the big bang when formation of nanostructures occurred in the early meteorites. Many different nanostructures were identified after that such as sea shells. The Scientific approach of nanomaterials started however was developed much later. Michael Faraday's study on colloidal gold particles is one of such scientific reports known. Besides this , It has been more than 70 years of investigation on nanostructured catalysts. Today nanophase building extends in a quickly developing number of basic and practical materials, both inorganic and natural, permitting control of mechanical, reactant, electric, attractive, optical and electronic capacities. The creation of nanophase or group amassed materials is generally founded on the formation of isolated little bunches which at that point are melded into a mass like material or on their installation into minimized fluid or strong network materials.

Organometallic and Coordination Chemistry: Fundamental and Applied Aspects International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, Nizhny Novgorod, Russia International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ORGANOMETALLIC AND COORDINATION CHEMISTRY: FUNDAMENTAL AND APPLIED ASPECTS INTERNATIONAL YOUTH SCHOOL-CONFERENCE ON ORGANOMETALLIC AND COORDINATION CHEMISTRY September 1-7, 2013 Volga and Sheksna rivers Nizhny Novgorod – Goritsy –Nizhny Novgorod, Russia Organizing committee: Prof. Gleb A. Abakumov (Chairman), Prof. Sergey M. Aldoshin, Prof. Valentin P. Ananikov, Prof. Mikhail Yu. Antipin , Prof. Irina P. Beletskaya , Prof. Mikhail N. Bochkarev , Prof. Vladimir I. Bregadze, Prof. Yury N. Bubnov, Prof. Anatoly L. Buchachenko, Prof. Vladimir K. Cherkasov (Vice Chairman), Prof. Oleg N. Chupahin, Prof. Vladimir P. Fedin, Prof. Igor L. Fedushkin, Prof. Dmitry F. Grishin , Prof. Mikhail P. Egorov, Prof. Igor L. Eremenko, Prof. Alexandr I. Konovalov, Prof. Vadim Yu. Kukushkin, Prof. Elena R. Milaeva, Prof. Ilya I. Moiseev, Prof. Aziz M. Muzafarov, Prof. Oleg M. Nefedov, Prof. Vladimir M. Novotortsev , Prof. Viktor I. Ovcharenko, Prof. Renad Z. Sagdeev, Prof. Elena S. Shubina, Dr. Klara G. Shalnova (Scientific Secretary), Prof. Oleg G. Sinyashin, Prof. Alexandr A. Trifonov Program committee: Gleb.A. Abakumov (chairman), Irina P. Beletskaya, Mikhail N. Bochkarev, Vladimir I. Bregadze, Yury N. Bubnov, Vladimir K. Cherkasov, Dmitry F. Grishin, Mikhail P. Egorov, Elena S. Shubina, Oleg G. Sinyashin International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE CONFERENCE IS SUPPORTED BY Russian Foundation for Basic Research Dynasty Foundation Russian Academy of Scienses Branch of Chemistry and Material Scienses of Russian Academy of Scienses International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Plenary lectures International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia FIFTY YEARS OF CARBORANE CHEMISTRY Vladimir Bregadze A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilov Str. 28, 119991, Moscow, RUSSIA. Fifty years ago the first papers on synthesis of icosahedral carboranes C2B10H12 have been published, and these publications opened a new page in chemistry history. Carboranes were shown to be important both from fundamental point of view and for practical perspective. In carboranes the unusual to that time two-electron three-centered and multi-centered bonds were realized. Carborane gave an example of three-dimensional aromatic compound (Fig. 1). ortho-carborane CH meta-carborane para-carborane BH Fig. 1 The history of carborane origin and development of this unusual and exciting field of chemistry are presented in the lecture. It is of interest that synthesis of icosahedral carboranes has been published in one time in USSR and USA in November-December issues of journals [1-4]. In USA two companies were involved to this project: Thiokol Chemical Corporation (Dr. M.S.Cohen, et al) and Olin Mathieson Chemical Corporation (Dr. T.L.Heying, et al). In USSR L.I.Zakharkin and coworkers from INEOS were authors of the first publications. I would like also to underline a great role of Prof. A.F.Zhigach and his coworkers in development of technology of boron hydrides and carboranes production. Theoretical works in the field of carborane and polyhedral borane structure have been made by Prof. W.N.Lipscomb [5] who became Nobel Prize Winner in 1976. Comprehensive monograph on carboranes was presented by Prof. R.N.Grimes [6]. 1. T. L. Heying, J. W. Ager, Jr., S. L. Clark, D. J. Mangold, H. L. Goldstein, M. Hillman, R. J. Polak and J. W. Szymanski, Inorg. Chem., 1963, 2, 1089-1092. 2. M. M. Fein, J. Bobinski, N. Mayes, N. Schwartz and M. S. Cohen, Inorg. Chem., 1963, 2, 1111-1115. 3. L. I. Zakharkin, V. I. Stanko, V. A. Brattsev, Yu. A. Chapovskii and Yu. T. Struchkov, Russ. Chem Bull., 1963, 12, 1911 [Izv. Akad. Nauk. SSSR, Ser. Khim. (in Russian), 1963, 2069]. 4. L. I. Zakharkin, V. I. Stanko, V. A. Brattsev, Yu. A. Chapovskii and O. Yu. Okhlobystin, Russ. Chem Bull., 1963 12, 2074 [Izv. Akad. Nauk. SSSR, Ser. Khim. (in Russian), 1963, 2238-2239]. 5. W.N.Lipscomb, Boron Hydrides, W. A. Benjamin Inc., New York, 1963. 6. R. N. Grimes, Carboranes; 1st ed., Academic Press: New York, 1970, 260 p.; 2nd ed., Academic Press (Elsevier), 2011, 1246 p. e-mail: bre@ineos.ac.ru PL1 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REVISITING OLD FAMILIES OF CYANO-BRIDGED COORDINATION POLYMERS AT THE NANOSCALE Y. Guari, a J. Larionova and J. Long a Institut Charles Gerhard, UMR 5253 CNRS-UM2-ENSCM-UM1, Chimie Moléculaire et Organisation du Solide, Université Montpellier II, Place Eugène Bataillon, 34095, Montpellier Cx 5, France. From 1704, year of the discovery of the oldest coordination polymer, Prussian blue, to now, many cyano-bridged coordination polymers were synthesised and extensively studied. This research field remains very active with the development of materials featuring magnetic, photomagnetic, sorption or catalytic properties. A signiﬁcant part of the current research Schematic representation of cyano-bridged coordination polymer based nanocomposites synthesis and their use in Cs decontamination. In addition, the ease of synthesis of these nanoparticles under mild conditions allows control of their size, shape and sometimes their organization and thus control over their properties. In this presentation, we will illustrate the latest developments made in our research groups on this topic. We will discuss various synthetic methodologies that we developed for the preparation of nano-objects or nano-composites of these materials and magnetic, magneto-optic or sorption properties associated therewith. activity on these materials is devoted to the synthesis and study of size and shape controlled cyano-bridged coordination polymer materials at the nanoscale.1 These nanomaterials have the same advantages as the corresponding bulk materials. Among them may be mentioned the versatility of precursors that can be assembled, the adjustable porosity and the possibility to combine several properties within a single nano-object by a judicious choice of precursors. Biomedical imaging using cyano-bridged coordination polymer nanoparticles. We will also address the potential applications of cyano-bridged coordination polymer nanoparticles and nanocomposites in the fields of medical imaging and decontamination of mobile radioactive elements. [1] A(a) S. P. Moulik, G. C. De, A. K. Panda, B. B. Bhowmik, A. R. Das, Langmuir 1999, 15, 8361; (b) S. Vaucher, M. Li, S. Mann, Angew. Chem., Int. Ed. 2000, 39, 1793; (c) J. Larionova, Y. Guari, C. Sangregorio, Ch. Guérin, New J. Chem. 2009, 33, 1177; (d) F. Volatron, L. Catala, E. Riviere, A. Gloter, O. Stephan and T. Mallah, Inorg. Chem., 2008, 47, 6584–6586. Acknowledgements – The authors thank the ANR, MAE-RAS, LR region, UM2 and ERA.Net-RUS program for financial support. e-mail: yannick.guari@um2.fr PL2 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CARBORANES AND METALLACARBORANES: A HISTORIC PERSPECTIVE Narayan S. Hosmane Department of Chemistry and Biochemistry, Northern Illinois University, Faraday Labs, Normal Road, DeKalb, IL 60115-2862, Fax: 815-753-4802, hosmane@niu.edu Most of the carborane derivatives of the icosahedral (C2B10) or small cage (C2B4) systems are formed by varying the groups on the cage carbons. This is usually accomplished in the original carborane synthesis by reacting substituted acetylenes with either the decaborane(14) or pentaborane(9) precursors. These reactions led directly to the “carbons adjacent” carboranes in which the carbon atoms occupy adjacent positions in the cage. The larger cages are obtained as closo-icosahedra, while the small cage, C2B4-carboranes, have nidostructures. In the small cage system there is another cage geometry in which the carbon atoms are separated by a boron atom. Although these “carbons apart” or nido-2,4(CR)2B4H6 species are thermodynamically more stable and are more symmetric than the “carbons adjacent” isomers, they are not as well studied. The main reason for the relative scarcity of information on the “carbons apart” systems lies in their method of preparation; they must be synthesized from their “carbons adjacent” analogues through a sequential series of oxidative cage closure/reductive cage opening reactions. In light of complete destruction of pentaborane stockpile at the US Edwards Airforce Base, we have also directed our attention to the development of a safe, bench-scale preparation of the small-cage carboranes, that does not require isolating and handling dangerous, volatile and toxic borane precursors, such as pentaborane(9). The historic perspective of the chemistry of carboranes and metallacarboranes along with the latest findings in our research involving boron nanomaterials will be presented in detail. Hosmane, N. S.; Maguire, J. A. Organometallics, 2005, 24, 1356-1389. Satapathy, R.; Dash, B. P.; Maguire, J. A.; Hosmane, N. S. Dalton Trans., 2010, 39, 6613-6625. PL3 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE MODULATION OF ORGANIC PHARMACOPHORE’S ACTIVITY BY THE INCORPORATION OF A METAL. A NOVEL WAY TO THE METAL-BASED PHARMACEUTICALS E. Milaeva Moscow State Lomonosov University, 603950, Leninsky Gory, 119991, Moscow, RUSSIA. The question if the metal is “boon or bane” in medicine has been answered by bringing a good deal of metal-based drugs to the pharmaceutical market in recent time. Nowadays there is a strong need of the design of novel potential therapeutic candidates based on organometallic and coordination metal compounds since the metal-based physiologically active substances posses a wide spectrum of activities. This short review will focus on a novel approach for the molecular construction of the target-oriented metal complexes combining in one molecule both an organic pharmacophore and a metal center. The synthesis and biological screening of organometallic compounds and metal complexes where metal is either a biogenic element (Fe, Mn, Cu, Co, Zn) or a pharmaceutically important metal (Pt, Ru, Sn, Sb) will be discussed. The metal is considered to play a key role in biomolecular mechanism of metal complex actions as antiprolifirative and neuroprotective agents. organic pharmacophore L[ M ] The assay has been performed by using model reactions (DPPH, CUPRAC-tests, liposome system), enzymatic methods (tubuline, lipoxygenase, xanthine oxidase, gluthathione reductase, thioredoxine reductase), in vitro and ex vivo lipid peroxidation in mitochondria and homogenates from Wistar rat brain and liver. The in vivo study and molecular doking were performed for the lead compounds. [1] E.R.Milaeva et al, Dalton Trans., 2013, 6817-6828. [2] I.I. Ozturk, A.K. Metsios, S. Orlova et al, Medicinal Chem. Research, 2012, 21, 3523-3531. [3] D.B. Shpakovsky, et al, Dalton Trans., 2012, 14568-14582. [4] E.R.Milaeva Current Topics in Medicinal Chem., 2011, 12, 2703-2713. [5] E.R.Milaeva, S.I. Orlova et al, Russian Chemical Bulletin, 2011, 60, 2564-2571. [6] E.R.Milaeva, S.I.Filimonova et al, Bioinorganic Chemistry & Applications, 2010, ID 165482. [7] E.R.Milaeva et al, Inorg. Chem., 2010, 49, 488-501. [8] E.R. Milaeva, N.N. Meleshonkova et al, Inorg. Chimica Acta, 2010, 363, 1455-1461. [9] M.N. Xanthopoulou, S.K. Hadjikakou, N. Hadjiliadis, E.R. Milaeva et al, Eur. J. Medicinal Chemistry, 2008, 43, 327-335. Acknowledgement: The financial support of RFBR (12-03-00776, 11-03-12088-ofi-m-2011, 11-03-01134), Program “Medicinal Chemistry” of Russian Academy of Sciences is gratefully acknowledged. e-mail: milaeva@org.chem.msu.ru PL4 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE UNIVERSE _ A GUIDE TO NEW CHEMISTRY Herbert W. Roesky Georg-August-University Goettingen, Institute of Inorganic Chemistry, Tammannstrasse 4, 37077 Goettingen, Germany In the interstellar space a number of compounds with low valent elements have been spectroscopically characterized. In our ongoing research we are trying to synthesize those compounds with low valent elements with the support of N-heterocyclic carbenes. Preferentially I will report the results on aluminum(1), silicon(0), silicon(I), silicon(II), germanium(I), and germanium(II). Compounds such as RAl: and :SiCl2 can be prepared and their striking properties are created through the metals, which function as Lewis bases as well as Lewis acids. Tailor-made N-heterocyclic carbenes are used for the stabilization of radicals and biradicals. The resulting products can be used for the activation of molecules, due to the radical or biradical centers in the coordination sphere of the metals. e-mail: hroesky@gwdg.de PL5 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THERMAL ACTIVATION OF METHANE BY METAL OXIDES IN THE GAS PHASE M. Schlangena and H. Schwarza a Technische Universität Berlin, Institut für Chemie, Straße des 17. Juni 115, 10623 Berlin, GERMANY. In terms of selective oxidation of hydrocarbons, oxygen-based systems represent a keystone in contemporary catalysis. However, a detailed mechanistic knowledge of the elementary processes is still rather limited. Thus, gas-phase chemistry of transition-metal oxide cations [MxOy]+ has received considerable attention with the aim to uncover mechanistic details of catalytic transformations [1]. Different types of methane activation by metal-oxide species have been observed in the gas phase, including hydrogen- as well as oxygen-atom transfer (HAT, OAT), and carbene as well as formaldehyde formation [2]. Examples of these types of reactions are described including mechanistic details, and properties of the reactive species are identified which are required to bring about the wanted transformation. For example, the bond-dissociation energy BDE(M+–O) determines the ability to transfer an oxygen atom to methane while relativistic effects play a role for carbene formation. Particular emphasis will be paid to the concept of oxygen-centered radicals, i.e. the presence or absence of a high spin density located at a terminal oxygen atom which turned out to be crucial for thermal HAT reactions [3]. [1] D. Schröder, H. Schwarz, Proc. Natl. Acad. Sci. USA, 2008, 105, 18114. [2] H. Schwarz, Angew. Chem. 2011, 123, 10276; Angew. Chem. Int. Ed. 2011, 50, 10096. [3] N. Dietl, M. Schlangen, H. Schwarz, Angew. Chem., 2012, 124, 5638; Angew. Chem. Int. Ed., 2012, 51, 5544. Acknowledgements - Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft (DFG), Cluster of Excellence “Unifying Concepts in Catalysis” (coordinated by the TUB and funded by the DFG), past and present co-workers of the Schwarz group. e-mail: maria.schlangen@mail.chem.tu-berlin.de PL6 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia Section Lectures International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia POLYNUCLEAR HALOGENIGE COMPLEXES OF BISMUTH AND POLYOXOMETALATES: SIMILARITIES, DIFFERENCES, SYMBIOSIS S.A Adonina,b, D.A. Mainicheva, S.G. Kozlovaa and M.N. Sokolova,b a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 630090, Lavrentieva st. 3, Novosibirsk, RUSSIA. Polyoxometalates (POM) and polynuclear halogenide complexes of Bi represent two large classes of coordination compounds; both attract a growing interest due to their promising properties, related to materials science and catalysis. Here we report our latest results in the chemistry of polynuclear bismuth iodides (PIBs) and a route to the creation of hybride POM complexes containing BiX3 (X = Cl, Br, I). Reaction of BiI3 and Bu4NI in acetone leads to formation of a new octanuclear PIB complex, TBA4[β-Bi8I28] (1). As other PIBs, this compound displays strongly prominent thermochromic behavior. To explain its nature, a combination of physical methods (XRD and DSC) and computational studies has been used. We found that the key role is played by the system of weak intramolecular I...I interactions which dramatically changes with the temperature due to slight thermal distortions of the whole anion structure [1]: The first PIB complex containing heterometallic octahedral unit, [Bi2PtI12]2- (2), has been obtained by reaction of H2[PtCl6], NaI and BiI3 [2]. The bonding was studied by DFT calculations. Reactions of (Bu4N)4[β-Mo8O26] with BiX3 (X = Cl, Br, I) in CH3CN lead to coordination of two BiX3 fragments, yielding in family of hybride [β-Mo8O26(BiX3)2]4- polyoxoanions (3-5): BiX3 CH3CN, 30 min We suppose that 3-5 will display catalytic activity of in oxidation of organic substrates; corresponding experiments are underway. [1] S.A. Adonin, M.N. Sokolov, P.A. Abramov et al., Chem. Eur. J. 2013, submitted [2] S.A. Adonin, M.N. Sokolov, A.I. Smolentsev et al., Dalton Trans. 2013, accepted manuscript Acknowledgements – RFBR (Grants No. 13-03-00012 and 13-03-01261a), Scholarship of President of Russia e-mail: adonin@niic.nsc.ru S1 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia PECULIARITY OF THE LUMINESCENCE MECHANISM OF Sm(III), Eu(III) and Yb(III) COMPLEXES M.N. Bochkarev, V.A. Ilychev and A.P. Pushkarev a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. To describe the luminescence mechanism of organo-lanthanide complexes the well-known Jablonski-Crosby energy diagram usually is used (Fig. 1). The scheme is consistent with the vast majority of experimental data but it does not explain the hyperemission of Yb(III) and the lack of Eu(III) luminescence in some recently obtained complexes with substituted phenolate and naphtholate ligands. 1 ligand S Ln [(L– )*Ln3+ (L– )2]2 – 3+ – [(L )Eu * (L )2]2 3 f1 * T f* ex c b b P NR S0 c a F NR [(L• )Yb2+(L– )2]2 [(L• )Eu2+ (L– )2]2 [(L– )Yb3+* (L– )2]2 e L e NR d f0 [(L– )3Ln3+]2 =982 nm h (1) (2) Fig. 1. Conventional mechanism of sensitized emission of lanthanide complexes (singlet state 1 S; triplet state 3T; excited state f*; fluorescence F; phosphorescence P; luminescence L; excitation ex; non-radiative pathways NR). Fig. 2. Redox mechanism of luminescence of lanthanide complexes (ligand excitation a; electron transfer from the excited ligand to Ln(III) b; back electron transfer from Ln(II) to the radical L with formation of excited Ln(III) c; relaxation and the metal-centered emission d; The alternative mechanism of excitation of Ln(III) (Fig. 2) comprising the stages of Ln(III) reduction to Ln(II) and the reverse process of oxidation of Ln(II) to Ln(III) due to the electron transfer from divalent ion to the radical ligand provides such an explanation. The latter step in this pathway in the case of Yb derivatives results in the formation of excited Yb(III) ions. Since the parity forbidden f-f transitions in these processes do not prevent the formation of excited Yb (III)* ions the efficiency of luminescence is unusually high. The energy level of excited Eu(III) ions is significantly higher than that of Yb(III), which does not allow to reach the excited state Eu(III)* and to get the metal-centered emission. Taking into account the values of Ln(III)/Ln(II) redox potentials for Sm (-1.50 V), Eu (-0.34 V) and Yb (-1.18 V) as well as rather low energy level of Sm(III)* one can suppose that the excitation of metal ions in the samarium complexes also can be achieved through the mechanism of the intramolecular electron transfer according to the scheme on Fig. 2. Acknowledgements – The work was supported by the Russian Foundation of Basic Research (Grants 13-0300097 and 13-03-97046) and Presidium of Russian Academy of Sciences (Program "Fundamental research of nanotechnologies and nanomaterials"). e-mail: mboch@iomc.ras.ru S2 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia MAGNETIC CONTROL OF THE DNA SYNTHESIS A. L. Buchachenko Institute of Chemical Physics, Russian Academy of Sciences, 119991 Moscow, Russia. DNA synthesis is known to occur by polymerases, magnesium-dependent molecular machines, which attach nucleotide three-phosphate monomer molecule to the growing DNA chain. Chemical mechanism of the attachment was traditionally thought to be nucleophilic which does not imply participation of any spin-carrying, paramagnetic intermediates. By using polymerases β loaded by pure isotopic ions 24Mg2+, 25Mg2+ and 26Mg2+ we have detected magnetic isotope effect: 25Mg2+ ions with magnetic nucleus 25Mg were shown to suppress enzymatic activity by 2-3 times with respect to that of polymerases β loaded by 24Mg2+ and 26 Mg2+ ions. No difference in enzymatic activity was found between polymerases β carrying 24 Mg2+ and 26Mg2+ ions with spinless, nonmagnetic nuclei 24Mg and 26Mg. The rate of DNA synthesis by polymerases β was also shown to exhibit magnetic field effect, in conformity with isotope effect. Polymerase chain reaction is also suppressed by 25Mg2+ ions. Both isotope and magnetic field effects indicate that in the DNA synthesis a new, ion-radical mechanism functions and coexists with generally accepted nucleophilic one. Magnetic control of the DNA synthesis may be used for medical purposes to regulate trans-cranial magnetic stimulation, gene expression, cell proliferation, biological clocks, apoptosis of the cancer cells, and many other processes related to the molecular functioning of living organisms.. S3 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia PROSPECTS OF SYNTHETIC ELECTROCHEMISTRY IN THE DEVELOPMENT OF UNUSUAL OXIDATION STATE METAL CATALYSTS FOR C-Cf AND P-Cf BONDS FORMATION REACTIONS AND HYDROGEN-EVOLVING ACTIVITY Y.H. Budnikovaa, Y.B.Dudkina, V.V. Khrizanforova, M.N. Khrizanforov, T.V. Gryaznova a A.E.Arbuzov Institute of Organic and Physical Chemistry, KSC of RAS, Kazan, RUSSIA Achievements of electrosynthesis mediated by nickel and palladium complexes in unusual oxidation states will be demonstrated. Important advances are associated with the development of synthetic approaches to the C = C, C-Hal, P-Cl, P-P and C-H bonds functionalization in the one-step mild conditions. The leading role of electrochemistry in the development of biomimetic catalysts for oxidation of hydrogen in the coordination sphere of the complex or H2 evolution will be discussed. The key intermediates, such as Ni(I)L, Pd (III)L(dimer or monomer complexes) and others have been detected and investigated. Acknowledgements - We thank Russian Foundation for Basic Research (grant N 13-03-97025, 13-03-00139, 11-03-92662) for the support of this work e-mail: a. yulia@iopc.ru S4 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SWITCHABLE MAGNETIC PROPERTIES IN PYRAZOLATE-BASED DI- AND TETRANUCLEAR COMPLEXES. S. Demeshkoa, S. Dechert, F. Fabbiani and F. Meyer a Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077 Göttingen, Germany. Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel dinuclear nickel(II) complexes [LNi2(N3)3]·(solvent)n that incorporate one bridging and two terminal azido ligands. Molecular structures have been elucidated by X-ray crystallography. One of the complexes exists in form of different polymorphs. Two polymorphic modifications of the molecular dinickel(II) complex [L1Ni2(N3)3] show thermal hysteresis of the magnetic susceptibility for single crystals, in which a 1,3-bridging azido ligand functions as an on/offswitch for the intramolecular antiferromagnetic coupling between the two metal ions. The switching function of the 1,3-bridging azide is closely connected to the order/disorder of the thioether arms and can be even blocked by appropriate chemical modification. The investigation of pressure effects on the magnetic bistability of [L1Ni2(N3)3] allows to shift the transition temperature more than 80 K towards higher temperatures. e-mail: sdemesc@gwdg.de S5 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia MULTIDECKER COMPLEXES OF RARE EARTH ELEMENTS WITH TETRAPYROLLIC LIGANDS: HOW MANY DECKS ARE POSSIBLE? Yu.G. Gorbunovaa,b, A.G. Martynovb, K.P. Birinb, M.A. Polovkovab, A.Yu. Tsivadzea,b a b N.S. Kurnakov Institute of General & Inorganic Chemistry of RAS, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskiy p.31, Moscow, 119991 RUSSIA The discovering of double-decker lanthanide sandwich complexes with unsubstituted phthalocyanine was made almost 50 years ago1. Over the years, the complexes of rare earth elements (lanthanides, except Pm, Y, Sc) with a variety of substituted macrocyclic tetrapyrrole ligands were synthesized2,3. These compounds are widely used as components of electrochromic displays, sensors, conductive materials, etc. In recent years a large number of triple-decker sandwich complexes containing two metal atoms and three tetrapyrrole ligands were investigated. Is it possible to further increase of decks numbers in sandwiches? Yes, it is possible in the case of weak non-covalent, supramolecular interactions. For, example, once the crown-ether groups are attached to the periphery of double- and triple-decker REE complexes, their properties can be tuned by molecular recognition of metal cations4. The report will be devoted to our recent investigations of elaboration of efficient and regioselective synthetic approaches towards heteroleptic crown-substituted REE complexes, including heterometallic complexes and their further thorough characterization (including studies of cation-induced assemblies)5,6. The approaches to the investigation of compounds in solution and solid state will be discussed7-10. Particular attention will be paid to the development of new functional materials based on the sandwich crownphthalocyaninates REE. 1. 2. 3. 4. Kirin S.P., Moskalev P.N., Makashev Yu.A., Rus. J. Inorg.Chem., 1965, 10, 1065. Pushkarev V.E., Tomilova L.G., Tomilov Yu.V. Russ. Chem. Rev., 2008, 77, 875. Jiang J. and Ng D. K. P., Acc. Chem. Res., 2009, 42, 79. Gorbunova Yu.G., Martynov A.G., Tsivadze A.Yu., Crown-Substituted Phthalocyanines: From Synthesis Towards Materials, chapter in Handbook of Porphyrin Science, Kadish K. M., Smith K. M., Guilard R.Eds., World Scientific Publishing, 2012, vol. 24, pp. 271–388. 5. Tsivadze A.Yu., Martynov A.G., Polovkova M.A., Gorbunova Yu.G. Rus. Chem. Bull., 2011, 11. 6. Birin K.P., Gorbunova Yu.G., Tsivadze A.Yu. Dalton Trans., 2011, 40, 11539. 7. Martynov A.G., Gorbunova Yu.G., Tsivadze A.Yu. Dalton Trans., 2011, 40, 7165. 8. Birin K.P., Gorbunova Yu.G., Tsivadze A.Yu. Dalton Trans., 2011, 40, 11474. 9. Birin, K.P., Gorbunova Yu. G., Tsivadze A. Yu. Dalton Trans., 2012, 41, 9672. 10. Smola S.S., Snurnikova O.V., Fadeyev E.N., Sinelshchikova A.A., Gorbunova Yu.G., Lapkina L.A., Tsivadze A.Yu., Rusakova N.V. Macroheterocycles, 2012, 5, 343. Acknowledgements - This work was supported by Russian Foundation for Basic Research (grant 11-03-00968), Russian Academy of Sciences and by Ministry of Education and Science of Russian Federation (agreement 8428). e-mail: yulia@igic.ras.ru S6 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURES AND UTILITY OF ORGANO-GALLIUM AND INDIUM COMPLEXES WITH OXO AND THIO LIGANDS Vimal K. Jain*, A. Wadawale, N. P. Kushwah and M. K. Pal Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 The chemistry of organo-gallium and -indium complexes with internally functionalised oxo-ligands and dithiolate has been explored. The reactions of triorgano-gallium and -indium etherate with a variety of internally functionalized oxo lignads such as anionic and dianionic Schiff bases [e.g., 2-hydroxy-Nsalicylideneaniline, 2-hydroxy-N-(2-hydroxy-3- methoxybenzylidene)aniline and 2-mercapto-N-salicylideneaniline] and benzoazole ligands [e.g., 2-(2′-hydroxyphenyl)-benzoxazole (Hhbo), 2-(2′-hydroxyphenyl)benzothiazole (Hhbt) and 2-(2′-hydroxyphenyl)benzimidazole (Hhbi)] yielded complexes of the types [RML]n and [R2ML]n (where R = Me, Et; M = Ga, In; L = deprotonated oxo ligand) in nearly quantitative yields [1,2]. These complexes have been characterized by elemental analysis, IR, UV−vis, and NMR spectroscopy. Several of these complexes have been structurally characterized. The nuclearity of these complexes depends on the nature of the metal atom and the ligand. Some of the gallium complexes exhibited polymorphism. Photoluminescence studies of these complexes showed that the quantum yield is always higher than that of the corresponding ligands due to reduced intermolecular interactions in complexes as compared to free ligands. With 1,1-dithiolate ligands both classical and organometallic complexes of gallium and indium, [M(SS)3], [RM(SS)2] and [R2M(SS)] (where R = Me or Et; M = Ga or In; SS = RCS2, ROCS2, R2NCS2 and (RO)2PS2) have been isolated. Indium dithiolate and selenolate complexes have been used as molecular precursors for the preparation of mono dispersed βIn2S3and In2Se3 nano-particles [3]. [1] N. Kushwah, M.K. Pal, A. Wadawale, V. Sudarsan, D. Manna, T.K. Ghanty and V.K. Jain, Organometallics, 31 (2012) 3836-3843. [2] M.K. Pal, N. Kushwah, D. Manna, A. Wadawale, V. Sudarsan, T.K. Ghanty and V.K. Jain, Organometallics, 32 (2013) 104 - 111. [3] R. K. Sharma, G. Kedarnath, N. Kushwah, M. K. Pal, A. Wadawale, B. Vishwanadh, B. Paul and V. K. Jain, J. Organomet. Chem. (in press). Tel: +91(22)2559 5095; e-mail: jainvk@barc.gov.in S7 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia COORDINATION CHEMISTRY OF 1,2-DICHALCOGENOLATO CARBORANE LIGANDS Guo-Xin Jin Department of Chemistry, Fudan University, 200433 Shanghai, China Half-sandwich transition metal complexes (Cp*M, Cp* = 5-C5Me5) are useful model compounds [1] in which one hemisphere of the coordination shell is blocked by the voluminous Cp* rings. In the protected space below the Cp* ligands, 1,2-dichalcogenolate carborane ligands can be accommodated, e.q. 16-electron “pseudo-aromatic” mono-nuclear rhodium and iridium complexes Cp*M(E2C2B10H10) [2] (M = Rh, Ir; E = S, Se), and they can be used as starting materials to react with low valence transition metal complexes to give heteronuclear complexes, such as, binuclear complexes: Cp*M[E2C2(B10H10)]Fe(CO)3, Cp*Rh[E2C2(B10H10)]W(CO)4 and Cp*Ir[E2C2(B10H10)]Rh(COD) (M = Rh, Ir; E = S, Se), trinuclear complexes {Cp*M[E2C2(B10H10)]}2Mo(CO)2, {Cp*M[E2C2(B10H10)]}2W(CO)2 and Cp*M[E2C2(B10H10)] [CO(CO)3]2, tetra-nuclear complexes: * * Cp*2Rh2[E2C2(B10H10)]3Rh2(CO), {Cp Ir[E2C2(B10H9)]} Rh2(COD){Cp Ir[E2C2(B10H10)]} which contain metal-metal bonds. C Ir E E C Ir Ir C [(COD)Rh(u-Cl)]2 THF Rh E C E C E E E C C C E Heating Tolluene Rh Ir B3 E Ir E C C E = S, Se Cp*Ir(E2C2B10H10) reacts with [(COD)RhCl]2 to form cis-{Cp*Ir[Se2C2(B10H10)]}2Rh and In refluxing toluene solution, the cisoid complex can be converted in more than 95% yield to corresponding transoid trans-{Cp*Ir[Se2C2(B10H9)]}Rh{[Se2C2(B10H10)]IrCp*} which contains a boron-iridium bond. References: [1] a). G-X. Jin, Coord. Chem. Rev. 2004, 248, 587; b). S. Liu, Y-F Han, G-X. Jin, Chem. Soc. Rev., 2007, 36, 1543; 2009, 38, 3419; c). X. Meng, G-X. Jin, Coord. Chem. Rev. 2010, 254, 1260; d). Z-J. Yao, G-X. Jin, Coord. Chem. Rev. 2013 in web (DOI: 10.1016/j.ccr.2013.02.004). [2] a). X. Wang, G-X. Jin, et al. Chem. Euro. J. 2007, 13, 188; b). G-X. Jin, J-Q. Wang, et al. Angew. Chem., Int. Ed. Engl., 2005, 44, 259; c). J-Q. Wang, G-X Jin, et al. Chem. Euro. J., 2005, 11, 7343; Chem. Euro. J., 2005, 11, 5758-5764; d). J-Q. Wang, G-X Jin, et al.ChemComm. 2006, 162, Chem. Commun., 2010, 46, 3556; e). Y-F. Han, W-G. Jia, Y.-J. Lin, G-X. Jin, Angew. Chem. Int. Ed., 2009, 48, 6234-6238; f). X-K. Huo, G. Su, G-X. Jin, Chem. Euro. J. 2010, 16, 12017; g). W.-B.Yu, Y.-F. Han, G.X. Jin, Chem. Euro. J. 2011, 17, 1863; h). Z-J. Yao, Y-J. Lin, G-X. Jin, Chem. Euro. J. 2013, 19, 2611; 1). Z-J. Yao, G. Su, G-X. Jin, Chem. Euro. J. 2011, 17, 13298. E-mail: E-mail: gxjin@fudan.edu.cn S8 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia ACTIVATION OF THE HYDROPEROXIDES FORMATION AND DECOMPOSITION BY THE 3D METALS MONO- AND POLYNUCLEAR CARBOXYLATES AND CARBOXYLATE-PYRAZOLATES G. Kamalova and S. Nefedovb a A.V. Bogatsky Physico-Chemical Institute of Ukrainian Academy of Sciences, 65080, Lyustdorfskaya doroga str., 80, Odessa, UKRAINE. b N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, GSP-1, Leninsky prospekt str., 31, scow, -71, RUSSIA. In the recent years, an active discussion about the analogy between pyrazolates and carboxylates metal complexes and, first of all, their chemical and magnetic properties (for example, see [1]), takes place. In this presentation, on the examples of the cyclohexene (CH) and the dibenzyl ether (DBE) liquid phase oxidation by air oxygen and hydrogen peroxide (H2O2), and transformations of the corresponding hydroperoxides and H2O2 decomposition, the catalytic properties of more than hundred mono- and polynuclear and homo- and heteroligand carboxylate, pyrazolate and carboxylate-pyrazolate complexes of Co, Cu, Ni, Zn, and Pd were examined. It is shown that the growth of Co complexes nuclearity, generally leads to an increase of the rate and depth of CH oxidation and the selectivity of products of its hydroperoxide (HPCH) further transformations. The close connections between the rates of HPCH decomposition and formation, as well as the H2O2 decomposition in the presence of the studied complexes were revealed and suggested that in these cases the formation and the gap of the O-O bonds takes place on the same "catalytic sites". The catalytic properties of the complexes with metal cores MPd or M2Pd in the DBE oxidation, to a first approximation, are similar to those of the corresponding complexes with the cores M2 and M3. Two groups of the catalysts of DBE alternative routes oxidation, its hydroperoxide (HP) decomposition and the benzaldehyde (BAld) and benzoic acid (BAc) formation were identified. The complexes of Cu, Fe, Co and Pd with DBE, BAld and BAc formed by oxidation of DBE, are first isolated and identified by XRA. The possible mechanisms of these complexes formation and their role in the studied processes are discussed. An attempt was made by the QSPR approach to reveal the key factors of the studied complexes’ structure and composition, determinant their catalytic properties. In the case of complexes with metal cores Pd, CuPd, NiPd, Cu2Pd and Co2Pd, the dependences between the rate of H2O2 decomposition and concentrations of substrate and catalyst (CAT) have an extreme character, which indicates a substantial passivation of the catalytic system at a certain ratio H2O2:Cat. For complexes with composition Cu2( -Piv)4L2 the nature of terminal ligands (L) significantly influences the activation energy of H2O2 decomposition (NEt3<CO(NH2)2<P 3<MeOH<PPh3<Hdmpz<OPPh3), whereas for the complexes with composition C 2(Piv)4L2 this tendency is virtually nonexistent. [1] R.G.Raptis et all. Eur. J. Inorg. Chem., 2008, 30, 4745. Acknowledgements - This work was executed in frame of the Projects of Joint Competitions «Ukrainian National Academy of Sciences–Russian Fund of Basic Researches» (№ 32-08, № 05-03-10) and «Ukrainian and Russian Funds of Basic Researches» (№ F53.3/008). e-mail: gerbert_kamalov@ukr.net, snef58@gmail.com S9 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia TRANSITION METAL COMPLEXES OF 1,5-DIAZA-3,7DIPHOSPHACYCLOOCTANES AS A PROMISING BASIS OF BIOINSPIRED MIMETIC CATALYSTS. A.A. Karasik, A.S. Balueva, E.I. Musina, O.G. Sinyashin A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center of Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan (RUSSIA) During the last two decads 1,5-diaza-3,7-diphosphacyclooctanes attracted a steady attention as available P,P-chelating ligands possessing relative conformational rigidity [1], and the recent discovery of electrocatalysts of hydrogen evolution and hydrogen oxidation among their nickel (II) complexes inspired a renaissance of the chemistry of these heterocycles containing intramolecular amines that mimic the function of hydrogenase enzymes[2]. The present survey of the coordination chemistry of 1,5-diaza-3,7diphosphacyclooctanes 1 shows the possibility of the targeted design of their transition metal complexes of various structures which possess the desired properties. Main types of these complexes are P,P-chelate monoligand (2) and bis-P,P-chelate bis-ligand complexes 3[1-3], but recently the varying of exocyclic groups of the ligands and the metals allowed to obtain cage binuclear complexes 4 where diphosphines 1 are bridging ligands. The introduction of pyridyl substituents to phosphorus atoms of complexes 3 ([M]=Ni [4a]) allowed to increase their catalytic activities in electrochemical hydrogen evolution [4b]; the testing of these complexes in fuel cells showed the increase of the cell power up to 55% [4b]. These results indicate the unexausted potential of 1,5-diaza-3,7-diphosphacyclooctanes ligands and the necessity of a wide screening of their metal complexes in various catalytic and electrocatalytic reactions. [1] a)A. A. Karasik, G. N. Nikonov Z. Obsch.Khimii, 1993, 63, 2775-2790; b) A. A. Karasik, R. N. Naumov et al. Polyhedron, 2002, 21, 2251-2256; c) A. A. Karasik, R. N. Naumov et al. Dalton Trans., 2003, 2209-2214; d) A. Karasik, R. Naumov et al. Heteroatom. Chem., 2006, 17,499-513 [2] D. L. DuBois, R. M. Bullock. Eur. J. Inorg. Chem. 2011, 1017-1027. [3] a) S. N. Ignatieva, A. S. Balueva, A. A. Karasik et al. Inorg. Chem., 2010, 49, 5407-5412; b) Ju. S. Spiridonova, A. A. Karasik et al. Phosphorus, Sulfur, Silicon and Relat. Elem., 2011, 186, 764-765. [4] a) E. I. Musina, I. D. Strelnik et al. Phosphorus, Sulfur, Silicon and Relat. Elem., 2013, 188, 59-60. b) Yu. H. Budnikova , V. V. Khrizanforova et al. Phosphorus, Sulfur, Silicon and Relat. Elem., 2013, 188, 84-90. Acknowledgements This work was supported by RFBR (No.13-03-00563- , 12-03-97083-r_povolzhie_a), President’s of RF Grant for the support of leading scientific schools (No.NSh-6667.2012.3). e-mail: karasik@iopc.ru S10 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FUNCTIONAL POROUS COORDINATION POLYMERS OF 3d METALS: MAGNETIC, SORPTION AND REDOX PROPERTIES S.V.Kolotilova, M.A.Kiskin,b A.S.Lytvynenko,a R.A.Polunin,a I.L.Eremenko,b V.M.Novotortsevb and V.V.Pavlishchuka a L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, 03028, Kiev, UKRAINE b N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 31, 119991, Moscow, RUSSIA Porous coordination compounds (PCPs) of 3d metals are considered as promising objects for creation of functional materials, such as materials with tunable magnetic properties, selective sorbents or catalysts of different reactions. In contrast to porous materials of other classes, the structure of PCPs can be easily modified and certain functional groups can be included, which opens the way for creation of compounds, possessing desired properties. The presentation contains the results of studies of three groups of PCPs: - compounds, bearing chiral centers, which show different absorption of optical isomers; - polymers, containing redox-active sites, which show electrocatalytic activity in dehalogenation of organic substrates; - compounds which magnetic properties can be modified by thermal treatment. Chiral PCPs Co(L1)(CH3OH)(H2O) (H2L1 = bis-2,4-(N-S-prolyl)-6-chlorotriazine), [Li(H2O)(EtOH)][Fe(Lact)(LactH)2], [Na(H2O)2][Fe(Lact)(LactH)2] (H2Lact = S-lactic acid), Co2(H2O)(L2)(pyridine)4 (H2L2 = trans-1R,2R-cyclopropanedicarboxylic acid) were synthesized. X-ray structures of these compounds were determined. Sorption of pure isomers of 2-S-butanol and 2-R-butanol by these complexes was studied. Analysis of sorption/desorption isotherms allowed to show the differences in interaction with these substrates. PCPs with redox-active sites {Fe2MO(Piv)6}{M'L2}1,5 were prepared by linking of trinuclear complexes Fe2MO(Piv)6 with mononuclear compounds M'L2 (M = Ni, Co; M' = Co, Ni; Piv = pivalate, L = Schiff base from isoniazide and 2-pyridinecarbaldehyde). It was shown by cyclic voltammetry (CVA), that M'L2 fragments could undergo reversible oneelectron process M'L20/-1 both in corresponding discrete complexes (in solutions) and being incorporated in PCPs (in suspensions). The cathodic current of this process grew at presence of halogen-containing substrates (CHCl3 or CF2Cl-CFCl2), which could evidence for electrocatalytic dehalogenation of these compounds. Due to co-existence of paramagnetism and ability to exchange volatile ligands or guest molecules, magnetic properties of PCPs can be modified. It was shown that magnetic properties of several PCPs (Co(L1)(CH3OH)(H2O), Co(Piv)2(4-ptz)(EtOH)2 and some others, where 4-ptz = tris-(4-pyridyl)triazine) significantly changed in the whole temperature range from 2 to 300 K upon their thermal desolvation. Acknowledgements - The study was partially supported by joint grant of the National Academy of sciences of Ukraine (No. 10-03-13(U)) and Russian Foundation for Basic Research (No. 12-03-90418), the Council on Grants at the President of Russian Federation (Program for Support of Leading Scientific Schools, NSh2357.2012.3), Russian Academy of sciences and the National Academy of sciences of Ukraine. e-mail: svk001@mail.ru, m_kiskin@mail.ru S11 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia HETEROLIGAND LANTHANIDE COMPLEXES WITH REDOX-ACTIVE LIGANDS: A REPORT ABOUT RECENT RESULTS S. Konchenko, M.Ogienko, N. Pushkarevsky Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090, Acad. Lavrentiev ave., 3, Novosibirsk, RUSSIA. The report is focused on reactions of a few Ln(II) and Ln(III) complexes (lanthanocenes, amides and diimine complexes) with a number of quinones (both in neutral and reduced anionic forms) and their derivatives kindly granted by colleagues from IOMC RAS: O O O N O O N etc. O OH HO The reactions were found to cause different redox processes and lead to the compounds with different coordination modes depending on the nature of Ln and other ligands. Some of the compounds obtained are represented below: Acknowledgements - The authors are grateful to the Russian Foundation for basic research (grants No. 12-0331530, 12-03-31759, 13-01-01088), and Federal target program "Kadry" (Contract No. 8631) for financial support. e-mail: konch@niic.nsc.ru, snkonch@googlemail.com S12 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia MULTIFUNCTIONAL CYANO-BRIDGED COORDINATION POLYMERS J. Longa, R. A. S. Ferreirab, L. D. Carlos b, Y. Guari a, J. Larionovaa a b Institut Charles Gerhardt – UMR 5253, Equipe CMOS, Université Montpellier II, Place Eugène Bataillon, 34095 Montpellier Cedex 5, FRANCE. Departement of Physics, CICECO, Universidade de Aveiro, 3810-193, Aveiro, PORTUGAL In the scope of multifunctional molecular materials, magneto-luminescent coordination polymers constitute a new class of promising materials for numerous applications such as telecommunications or luminescent imaging. In this regard, cyano-bridged coordination polymers incorporating lanthanide ions can exhibit strong magnetic interaction between the spin carriers as well as high magnetic anisotropy. In addition, the lanthanide ions can also exhibit strong luminescence with well-resolved emission bands and long lifetimes. The self-assembly reaction between the paramagnetic cyanometallate core [M(CN)8]3- (M = Mo, W) and a lanthanide ion Ln3+, yields to a bi-dimensional Ln(H2O)n[M(CN)8] coordination network presenting a long-range ordering and the characteristic luminescence of the lanthanide ion.[1] In order to enhance the luminescence properties, it is possible to introduce antenna ligand in the coordination sphere of the lanthanide ion yielding to a onedimensional coordination polymer emitting in the Near-Infra Red region. [2] [] E. Chelebaeva, J. Long, J. Larionova, R. A. S. Ferreira, L. D. Carlos, F. A. Paz, A. Trifonov, J. B. R. Gomes, C. Guérin,Y. Guari, Inorg. Chem., 2012, 51 9005. [2] J. Long, E. Chelebaeva, J. Larionova, Y. Guari, R. A. S. Ferreira, L. D. Carlos, F. A. Almeida Paz, A. Trifonov, C. Guérin, Inorg. Chem., 2011, 50, 9924. e-mail: jerome.long@univ-montp2.fr S13 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia HOMO- AND HETERONUCLEAR TRANSITION METAL COMPLEXES PRODUCED BY DEPROTONATION OF PYRAZOLE AND ITS ANALOGUES S.E. Nefedov N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky pr,31, Moscow, RUSSIA Systematic studies of reactions of pyrazole and its analogues with carboxylates of 3d transition metals, palladium and platinum are presented. Key point in these reactions is the deprotonation of the pyrrole NH fragment. The pyrazolate anion that formed coordinates the metal atoms, producing pyrazolate-bridged homo- or heterometallic compounds. The composition and structure of the complexes obtained are determined by the metal nature, donor ability of the carboxylate anion and R’, R” groups at 3,5 position of the pyrazole cycle. {MX2} PzH R' R" R' N N H M {M'X2} -HX H+ M R" N N M' basicity of pyridine nitrogen atom X = OOCBut > OOCMe > OOCPh R'/R" = Me/Me , CF3/Me, H/H, CF3/CF3 strength of corresponding acid acidity of pyrrole fragment NH Acknowledgements- This work was supported by RFBR (projects 11-03-00824, 11-03-01157, 12-0331339, 13-03-90412) and the Presidium of the Department of Chemistry and Materials Science, Russian Academy of Sciences, and the Council for Grants of the President of the Russian Federation (MK-4452.2013.03) e-mail: snef@igic.ras.ru S14 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia CHEMICAL DESIGN OF CHALCOGEN-CONTAINING ORGANOMETALLIC CLUSTERS A.A. Pasynskii, Yu.V. Torubaev, I.V. Skabitsky, S.S. Shapovalov, A.V. Pavlova a N.S.Kurnakov Institute of General and Inorganic Chemistry, Moscow,Russia. The chalcogen-containing organometallic complexes were used as ligands to complexes of different transition metals (M). X-Ray analyses data showed the common features: a) sharp shortening (from 0.15 to 0.3 A) of formally ordinary M-E bonds (E = S, Se, Te) and M-P bonds[1] compared to the covalent radii sum (CRS) [2] ; b) electron-compensating rearragment of clusters. 1. The coordination of Fc2Te2 (Fc – ferrocenyl) and dissociation of Te-Te bond: Fc UV hexane, -10o C Te M(CO)4 (OC)4M -2CO Te M=Cr, Mo, W Fc 2. The coordination of CpFe(CO)2TePh. Fe+ OC OC Fe Te OC Fe CO CO Te CpFe(CO)3+ ClRe(CO)3(THF)2 2 CpFe(CO)2TePh - 2CO CO THF CO Re Fe OC CO Te OC Fe Cl Cr(CO)5(THF) [CpMn(CO)2]2(E2)[Cr(CO)5]2 (PPh3 )2 Pt(Ph2C2 ) (PPh3) 2Pt(Ph2C2) Mn CO I CO Ph3P MnI E II Pt E CO I CO Mn CO CO Ph3P PPh3 II Pt S . [1] A.A. Pasynskii , Russ. J. Coord. Chem., 2011, Vol. 37, No. 11, p. 801. [1] Cordero, B., Gomez, V., Platero-Prats, A.E., et al., Dalton Trans., 2008, p. 2832 e-mail: aapas@rambler.ru S15 S CO OC PPh3 CO CO 3. The coordination and transmetallation of [CpMn(CO)2]2E2 (E = S, Se, Te) [CpMn(CO)2]2(E2) Te Cr CO CO CO International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SLOW MAGNETIC RELAXATION AND PHOTO-INDUCED ELECTRON TRANSFER IN TETRATHIAFULVALENE-BASED COMPLEXES OF LANTHANIDES F. Pointillarta, G. Cosquera, Boris Le Guennica, S. Golhena, O. Cadora, O. Mauryb and L. Ouahaba a Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1 263 Avenue du Général Leclerc 35042 Rennes Cedex, FRANCE. b Laboratoire de Chimie, UMR 5182 CNRS-ENS Lyon-Université Lyon 1, 46 Allée d’Italie, 69364 Lyon Cedex 07, FRANCE Lanthanide complexes exhibit magnetic hysteresis and luminescence with very long lived excited state lead to potential application in quantum computing, spintronic, OLED, biomedical imaging…[1][2] Our approach consists in the combination of Dy(III) and Yb(III) ions to redox active Tetrathiafulvalene (TTF) ligands to elaborate Single Molecule Magnet (SMM) and Single Ion Magnets (SIM) involving multi physical properties. [Dy(hfac)3(L1)] (L1 = 4,5-bis(propylthio)-tetrathiafulvalene2-(2pyridyl)benzimidazole) displays a SIM behaviour only in solution while [Dy(hfac)3(L2)] (L2 = 4,5-bis(propylthio)-tetrathiafulvalene- 2-(2-pyridyl)benzimidazole-methyl-2-pyridine) is a SIM in both solution and solid-state. The SIM behaviour is obtained if the hydrogen bond is broken by dissolution or by alkylation. Multiple relaxation processes were identified for [Dy(hfac)3(L2)] with two competing processes: fast one acting in zero field and slow one acting for high field. Both processes cohabit for intermediate field. Magnetic dilution and frozen solution measurements drive us to conclude that the origin of these multiple relaxation processes is not due to the property of one single molecule.[3] Irradiation in the intra-ligand charge transfer bands provoked the Yb(III) luminescence in both [Yb(hfac)3(Ln)] complexes. The alkylation enhanced the two intensity and lifetime of the Yb(III) luminescence. The shape of the Yb(III) luminescence spectra is directly correlated to the energy splitting of the MJ states coming from the 2F7/2 multiplet ground state. Yb(III) luminescence process can involved a photo-induced electron transfer from the excited Ln chromophores to the Yb(III) ion making them good candidates for photo-induced conduction.[4] Finally, we will show through the study of a redox-active luminescent single molecule magnet that the two infrared-luminescence and dynamic magnetic properties can be correlated.[5] [1] L. Bogani and W. Wernsdorfer, Nat. Mater. 2008, 7, 179. [2] J-C. G. Bünzli and S. V. Eliseeva, Chem. Sci., 2013, 4, 1939. [3] G. Cosquer, F. Pointillart, S. Golhen, O. Cador, L. Ouahab, Chem. Eur. J., DOI:10.1002/chem.201300397. [4] G. Cosquer, F. Pointillart, B. Le Guennic, S. Golhen, O. Cador, O. Maury, L. Ouahab, submitted. [5] F. Pointillart, B. Le Guennic, S. Golhen, O. Cador, O. Maury, L. Ouahab, Chem. Commun. 2013, 49, 615. Acknowledgements - This work was supported by the CNRS, Rennes Métropole, Université de Rennes 1, Région Bretagne and FEDER. e-mail: fabrice.pointillart@univ-rennes1.fr S16 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia CHEMISTRY OF BORON HYDRIDES ORCHESTRATED BY DIHYDROGEN BONDS E.Shubina, O. Filippov, I. Golub A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences Moscow, Russia An increasing application of polyhedral boron compounds in medicine induced the intensive investigations of their interaction with biomolecules. One type of such interactions determining the polyhedron behavior in vivo is hydrogen bonding of polyhedral boron compounds with acidic and basic sites of biomolecules. The results of systematic investigation of intermolecular interactions of boron compounds – borohydrides, their derivatives containing organometallic fragments, carboranes, metallocarboranes, aminoboranes with different proton donating and proton accepting centers (hydrogens of B-H, C-H groups in polyhedron, OH, NHR substituents) will be presented in this communication [1-3]. Transition metal coordination compounds containing the borohydride ligand as BH4 or LBH3 (L = amine, phosphine) possess many valuable properties and useful applications. Thus, they have been used as selective reducing agents, as building blocks for the synthesis of new organometallic derivatives, as precursors for the production of borides, hydrides and other inorganic materials, as well as in hydrogen production. Herein we report on the reactivity of a variety of metal complexes, i.e. [(R3P)2Cu(2-BH4)], [(triphos)Cu(1-BH4)], [(triphos)RuH(2-BH4)], [(PP3)RuH(1-BH4)] (PP3 = 4-P(CH2CH2PPh2)3, triphos = 3CH3C(CH2PPh2)3) and [Ir(PCy3)2(H)2( 2-H2B(H)NR3)]+ [BAr4F]− complexes (R = H, alkyl) as well as of simple boron hydrides (BH4, BH3NR3) towards mono and bidentante XH acids of different strength. It was studied by variable-temperature IR, UV-vis and NMR spectroscopies in low polar solvents (CH2Cl2, THF) in combination with DFT calculations. Availability of several types of hydride ligands (MH, BHterm, BHbr) leads to multiplicity of reaction intermediates (mono-, bi- and trifurcate DHB complexes).The influence of coordination to the metal on the BH proton accepting ability mechanism of the reactions involving proton transfer as a key step will be discussed. Crutial role of additional Lewis acidic centers in the reactivity of transition metals borohydride complexes will be shown. DHB TS Acknowledgment: This work was supported by Russian Foundation for Basic Research (projects 12-03-33018, 13-03-00604 and 12-03-31176) 1. O. A. Filippov, N. V. Belkova, L. M. Epstein, A. Lledos, E. S. Shubina Comput Theor Chem 2012, 998, 129-140. 2.I.E. Golub, O. A. Filippov, E. I. Gutsul, N. V. Belkova, L. M. Epstein, A. Rossin, M. Peruzzini, E. S. Shubina Inorg. Chem. 2012, 51, 6486-6497 3. O. A. Filippov, N. V. Belkova, L. M. Epstein, E. S. Shubina J. Organometal Chem, 2013 S17 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia THERMALLY AND LIGHT INDUCED PHASE TRANSITION IN Cu(hfac)2 COMPLEXES WITH tert-BUTYLPYRAZOLYLNITROXIDES E. Tretyakov, M. Fedin, S. Tolstikov, A. Suvorova, I. Drozdyuk, G. Romanenko, A. Bogomyakov, R. Sagdeev and V. Ovcharenko International Tomography Center, Russian Academy of Sciences, 630090, Institutskaya str., 3a, Novosibirsk, RUSSIA. We succeeded in the synthesis of Cu(hfac)2 polymer-chain complexes with tert-butylpyrazolylnitroxides (RAlk). It was found that temperature variation leads to switching of N N complexes [Cu(hfac)2RMe]n and [Cu(hfac)2REt]·0.5Solv (Solv N N = C6H14, C7H16) between two structural and spin states: (A) Alk RAlk Alk L Alk elongated CuO6 octahedral units with axial Cu1-O1 distances, Alk = Me, Et, Pr weakly exchange-coupled heterospin clusters, (B) elongated CuO6 octahedra with equatorial Cu1-O1 distances, strongly exchange-coupled heterospin clusters. Illumination of [Cu(hfac)2RMe]n with light (~540 nm) at cryogenic temperatures leads to switching of the clusters from the spin state B to A, which relax to the ground state on a timescale of hours. O N O eff(B.M.) A 2,6 2,4 2,2 2,0 1,8 B 0 50 100 150 200 250 300 T (K) Et Figure 1. Fragments of the [Cu(hfac)2(R )]n chains and experimental dependences eff(T) for [Cu(hfac)2(NPzMe)] (■), [Cu(hfac)2(NPzEt)]·0.5C7H16 (▼), [Cu(hfac)2(NPzPr)] (●) at 1.0 T. Contrary to the complexes [Cu(hfac)2RAlk]n, their structural analogs with diamagnetic ligands LAlk do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and Cu(II) ions for the origin of magneto-structural anomalies in this family of molecular magnets. Acknowledgements - The study was supported by the Ministry of education and science of Russian Federation (project 8436), the Russian Foundation for Basic Research (grant nos. 11-03-00158, 12-03-33010, 12-03-00067, 12-03-31028, 12-03-31396), President grants ( -6497.2012.3, -1662.2012.3, MK-5791.2013.3), the Russian Academy of Sciences, and the Siberian Branch of RAS. e-mail: tev@tomo.nsc.ru S18 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia ORGANIC LIGHT EMITTING DIODES AND INORGANIC QUANTUM DOTS A.Vitukhnovsky, A.Vaschenko, S.Ambrozevich, A.Katsaba, A.Seliukov P.N.Lebedev Physics Institute of Russian Academy of Sciences 119991 Leninsky Pr., 53, Moscow, RUSSIA Currently there are intensive studies of new composite nanomaterials, as well as photonic and optoelectronic devices based on hybrid nanostructures [1, 2]. This report presents results of investigations of organic light-emitting diodes (OLED) with colloidal semiconductor quantum dots CdSe / CdS and CdSe / CdS / ZnS used as light emitters. We theoretically demonstrated a strong influence of quantum effects on spectral and electronic properties of device. Namely, there is a strong increase of energy transfer rate from excited state of organic molecules to quantum dots on decrease of either CdSe nanocrystal core diameter or CdS shell thickness. Decreasing of CdS core size from 5 to 3 nm leads to the transfer rate increase by an order of magnitude. Based on the theory, we fabricated a novel type of hybrid nano-emitters - a mixture of multilayer CdSe / CdS / ZnS quantum dots in conjunction with specially synthesized conductive polymers. The polymers having bithienyl fragment were additionally modified with amino groups. Such a composition provides good complex formation and allows to fabricate highly uniform thin films. Finally, the quantum dots linked with polythiophene derivatives exhibit bright electroluminescence when embedded in organic light emitting diodes. Results of these investigations are presented. Besides that we investigated bare-core CdS semiconductor nanocrystals with an average diameter 4.5 nm, which were passivated with oleic acid. Photoluminescence spectra measured with 405 nm laser excitation exhibit strong luminescence of surface states. Further investigations to find out an origin of the luminescence are presented and discussed. It is concluded that surface state luminescence offers an opportunity to fabricate white light organic light emitting diodes, where narrow emission of interband recombination in quantum dot is accompanied with broad luminescence of defect states. The results of our research demonstrate the possibility of effective control the spectral characteristics and energy transfer rates in nanophotonic devices based on semiconductor quantum dots embedded into organic matrix. [1] . . [2] . . , . . . , . . ., Ж , 2013, 4, in press. Ф, 2012, 96(2), 118. Acknowledgements The work was supported by LLC "OPTOGAN - Organic light solutions," contract number 45, and partially supported by RFBR, grant 12-03-00839-a e-mail: alexei@sci.lebedev.ru S19 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia Synthesis & Reactivities of Divalent and Trivalent Nickel Complexes Based on Pincer Ligands Davit Zargarian, Department of Chemistry, Université de Montréal Many pincer complexes have found applications in catalysis thanks to their enhanced thermal stabilities and the novel reactivities they promote. Our group has introduced a variety of pincer-type nickel complexes based on symmetrical or unsymmetrical ligands featuring amine, imine, phosphine, phosphinite, imidazolophosphine, imidazoliophosphine, or NHC-carbene donor moieties. Some of these complexes show good thermal stabilities and promote interesting reactivities, including Kumada coupling, alcoholysis and amination of acrylonitrile, fluorination of alkyl chlorides, and hydrosilylation of olefins, alkynes, and carbonyl substrates. This presentation will describe the synthesis, structures, and reactivities of divalent and trivalent pincer complexes of Ni. Selected references : (a) B. Vabre, Y. Canac, C. Duhayon, R. Chauvin, D. Zargarian, Chem. Comm. 2012, 48 (84), 10446. (b) B. Vabre, M. L. Lambert, A. Petit, D. H. Ess, D. Zargarian, Organometallics 2012, 31, 6041. (c) D. Zargarian, A. Castonguay, D. M. Spasyuk, Topics in Organometallic Chemistry 2012, 40, 131; ed. G. van Koten & D. Milstein. (d) D. M. Spasyuk, S. I. Gorelsky, A. van der Est, D. Zargarian, Inorg. Chem. 2011, 50, 2661. S20 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia Oral Presentations International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SOME HIGH COORDINATION COMPOUNDS OF LANTHANIDES(III) DERIVED FROM SCHIFF BASES Ram K. Agarwal Department of Chemistry, Lajpat Rai Postgraduate College, Sahibabad-201005 (Ghaziabad), INDIA Initially coordination chemistry of lanthanides was limited to strongly chelating ligands with oxygen as donor atom. With the development of new complexing compounds, a significant number of lanthanide complexes with various types of ligands were synthesized and characterized. The chemistry of metal complexes with heterocyclic compounds containing nitrogen, sulfur and oxygen as complexing ligands has attracted increasing attention. These compounds are worth attention for many reasons due to their biological activities while many drugs involve heterocycles, sulfur, oxygen, nitrogen, amino-nitrogen, azomethine-nitrogen and alcoholic or phenolic-oxygen are some of the donor atoms of interest. Pyrazolones (Nheterocyclic compounds) is an active moiety as a pharmaceutical ingredient, especially in non-steroidal anti-inflammatory agents used in the treatment of arthiritis and other musculoskeletal and joint disorders. Earlier work reported that some drugs showed increased activity when administered as metal-chelates rather than as simple organic compounds. Lanthanides constitute an interesting group of 15 elements with similar physico-chemical properties which change periodically with the atomic number. Lanthanide compounds frequently have magnetic, catalytic and optic properties and therefore they are widely used in industries. In recent years new experimental methods have been developed due to which new data on the role of lanthanides in the biochemical processes operating in cellular membranes organelles and cytoplasm have been obtained. The coordination compounds formed by lathanides(III) generally display the coordination number varies from six to twelve with different geometries. In present lecture, the author reports the summary of the work mostly carried out in our laboratory on lanthanide(III) complexes of Schiff bases derived from 4aminoantipyrine and their properties. [1] Ram K. Agarwal and Vinesh Kumar, Phosphorus, Sulfur and Silicon, 2010, 185, 1469-1483. [2] Ram K. Agarwal, H. Agarwal, S. Prasad and Anil Kumar, J. Korean Chem. Soc., 2011, 55, 594-602. [3] Ram K. Agarwal, S. Prasad and Upma Singh, Int. J. Chem., 2012, 1, 264-280. e-mail: ram_agarwal54@yahoo.com O1 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia OXYGEN-FREE CONVERSION OF METHANE V. Akhmedov M. F. Nagiyev Institute of Chemical Problems of Azerbaijan National Academy of Sciences, AZ1143, G. Javid Av. 29, Baku, AZERBAIJAN One of the most intriguing goals of specialists working in catalysis is to convert methane into valuable and transportable chemicals. Aside from oxidative rearrangements some successful attempts to upgrade methane into higher hydrocarbons have been reported in the last few years. We have employed the metal vapor method (MVM) for design of the novel catalytic materials containing on the support surfaces different combinations of layered transition metals (Ni, Co, Re, Rh, Ru, Pt, and Mo) on their atomically dispersed state. As established in our laboratory, MVM-prepared catalysts possess high C-H and C-C bond insertion ability, which causes the hydroconversion of hydrocarbons under very mild temperatures (400-480K). Here we describe and discuss the results of non-oxidative conversion of methane over MVM-prepared catalysts. Methane reacts with the most of MVM-prepared catalysts under mild conditions (normal pressure, 450-570K). In the first stage of interaction, methane forms CHx species on the catalyst surface, which can be condensed into C2-C6 alkanes at the same temperature range by hydrogen treatment. Combination of Ru with Re and Pt gave best results. Coupling of the accumulated on the catalyst surface CHx species can be promoted also by passing a mixture of CO+H2 through the catalyst. The selectivity of the methane coupling process can be regulated by the reaction temperature and nature of the active metals. Increasing the reaction temperature up to 973-1073K causes the one stage catalytic conversion of methane. Benzene was the main reaction product (85-95%) along with small amounts of ethylene, ethane, and toluene. Among the studied MVM-prepared catalysts MoZSM-5 systems were the most effective. Methane conversion on these catalysts achieved up to 7-7.5%. Activity and stability could be improved significantly by modification of MoZSM-5 samples by other metals such as Co, Re, Ru, Rh and Pt. This reaction seems to be one of the promising routes for practical utilization of methane. e-mail: advesv@gmail.com O2 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND LUMINESCENT PROPERTIES OF IRIDIUM-CONTAINING NORBORNENE-BASED COPOLYMERS Yu.E. Begantsova G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Iridium(III) compounds have attracted considerable attention due to their efficient electroluminescent properties. In the present work novel phenylpyridine Ir(III) complexes with norbornenyl-substituted pyrazolonate ancillary ligands were synthesized and structurally characterized: Compound 1 and 2 were copolymerized with carbazole-functionalized norbornene by ringopening metathesis polymerization. Photoluminescent spectra of synthesized Ir(III)-containing copolymers consist of broad bands in the region of 483-522 nm assigned to metal to ligand charge transfer transition. The relative quantum yields were found to be in the range of 1.0-8.4 %. Light-emitting diodes with the configuration of ITO/Ir(III)-copolymer/BATH/Alq3/Yb produced yellowish-green light. Maximum brightness of 986 cd/m2 and current efficiency of 2.20 cd/A were reached. Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Project No 1203-31154- mol-a) e-mail: bega@iomc.ras.ru O3 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FINE-TUNING OF CAGE-LIKE METALLASILOXANES SYNTHESIS. PECULIARITIES OF STRUCTURES AND MAGNETIC PROPERTIES. A. Bilyachenkoa, M. Dronovaa, A. Korlukova, J. Larionovab, J. Longb, E. Shubinaa, M. Levitskya a Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str., 28, Moscow 119991, RUSSIA b Université Montpellier 2, Bat. 17, Place Eugène Bataillon, 34095 Montpellier Cedex 05, FRANCE The phenomenon of cage-like metallasiloxanes synthesis’ fine tuning was established. It was found that changing of solvents system and/or stoichiometric (“magic”) ratio between interacted polyphenylmetallasiloxane and sodium phenylsiloxanolate gave an opportunity of isolation of cardinally different in their structure cage products. Determination of structural features and stacking’ style of cages in crystal lattice (which is strongly depends on nature of solvates used) were made by the X-ray. Peculiarities of molecular magnetism of synthesized cages (including first observation of single molecular magnet behaviour for cage-like metallasiloxanes) were studied in details. This work was supported by the Russian Foundation for Basic Research (grant No. 11-03-00646) e-mail: bilyachenko@ineos.ac.ru O4 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia ELECTROLUMINESCENT PLATIMUM-CONTAINING COPOLYMERS ON THE BASE OF FUNCTIONALIZED NORBORNENE MONOMERS L.N. Bochkarev G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. A series of norbornene-based platinum-containing copolymers were synthesized by ringopening metathesis polymerization and characterized by elemental analysis, NMR, IR, GPC, DSC, TGA. A representative synthesis of Pt-copolymers is shown in the scheme: N N Cl Cl Ru N CH 3 m C O N + n N Br O N Pt N O Ph n m N Br C=O CH 3 N N N O Pt N O The examples of the obtained copolymers are shown in the chart: All the copolymers are air stable solids well soluble in THF, CH2Cl2 and CHCl3. Photophysical and electroluminescent properties of the synthesised Pt-copolymers were studied. The emission bands in the region of 470-550 nm in photoluminescence and electroluminescence (EL) spectra can be assigned to metal to ligand charge transfer transition. The color of EL was found to depend on the composition of Pt-copolymers and changed from green to orange to white. Maximum brightness of 400 cd/m2 was reached. Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Project No. 1203-00250- ) e-mail: lnb@iomc.ras.ru O5 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia MAGNETO-STRUCTURAL CORRELATIONS IN 3d METAL COMPLEXES WITH SUBSTITUTED IMINONITROXIDES A.S. Bogomyakov, O.V. Kuznetsova, E.Yu. Fursova, E.V. Tretyakov, A.V. Polushkin, G.V. Romanenko, V.I. Ovcharenko International Tomography center, Siberian Branch of the Russian Academy of Sciences, 630090, Institutskaya str, 3a, Novosibirsk, RUSSIA. Iminonitroxides (INs) are widely used in design of magnetoactive compounds because of exchange interactions between spins of paramagnetic metal ions and coordinated by N atom IN fragments are strongly ferromagnetic. In some cases complex formation reactions are accompanied by a reduction of INs into corresponding aminonitrons (ANs), and ANs can be involved in complex formation. O O N R N [H] R N N H IN AN Structural differences of INs from ANs small, but are. Revealing of ANs in the complexes by X-ray allowed to avoid a misinterpretation of magnetic properties. O HO N O HO N N H N HLIN NO2 HLAN NO2 We found that interaction of 3d metal pivalates with (2-hydroxy-5-nitro-phenyl)iminonitroxide (HLIN) leads to heterospin complexes with both LIN and LAN as a ligands. The [Co3(LIN)2(LAN)2(Piv)2]•Me2CO•C7H16 complex demonstrates behaviour of a soft magnet at low temperature with spontaneous magnetisation at 2 K is about 36700 G·cm3/mol. eff (B)  (G cm /mol) 3 10.0 40000 9.5 20000 9.0 0 T = 2K -20000 8.5 -40000 8.0 0 100 T (K) 200 -60000 -40000 -20000 300 0 20000 40000 60000 H (Oe) Acknowledgements – The study was financially supported by the The Ministry of education and science of Russian Federation (project 8436), RFBR (12-03-31028, 12-03-31118, 12-03-00010), MK-6497.2012.3, RAS and SB RAS. e-mail: bus@tomo.nsc.ru O6 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia REDOX-ISOMERIC TRANSFORMATIONS. ELECTRONIC AND LATTICE CONTRIBUTIONS. M. Bubnova, N. Skorodumovaa, A. Zolotukhina, A. Arapovaa, N. Smirnovab, V. Cherkasova, A. Luk’yanovc, V. Travkinc, G. Pakhomovc a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b Chemistry Research Institute of N.I. Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina av. 23/5,Nizhny Novgorod, RUSSIA. c Institute for Physics of Microstructures of Russian Academy of Sciences, 603950, GSP-105, Nizhny Novgorod, RUSSIA. Redox-isomerism phenomenon in bis-quinonato cobalt compounds is the reversible metalligand electron transfer accompanied by spin-crossover of cobalt ion. Redox-isomerism occurring in solid state is extensively studied because of it possible application in microelectronics. The main regularities determining redox-isomeric equilibrium in general are known. We have already investigated the influence of the nature of quinonato ligand on the redoxisomeric equilibrium [1]. We have shown how the difference between 2,2’-dipyridine and 1,10-phenanthroline (two carbon atoms) change the temperature and steepness of transition [2]. The last two compounds are isostructural which allow to obtain solid solutions of variable composition. Solid solutions also demonstrate phase transitions accompanying redox-isomeric transformations. Thermodynamic parameters of phase transitions correlate with solid solution composition. Recently we have obtained three binuclear bis-semiquinonato cobalt complexes where the tetradentate neutral N-donor ligand play a role of bridge. Complexes differ one from another by quinonato ligands. Surprisingly that the transition temperature in this case does not depend on the nature of quinonato ligand. The only steepness of transition changes upon coming from one complex to another. We have successfully produced polycrystalline films of some redox-isomeric complexes by thermal vacuum deposition [3]. It was shown that electric conductivity of polycrystalline films and crystal samples of redox-isomeric complexes nonlinearly depend on a temperature. Temperature dependence of electric conductivity has maximum which temperature interval coincides with interval of redox-isomeric transformation. [1] G.A.Abakumov et al., Rus. J. Phys. Chem. , 2008, 82, №2, 172-176. A.V.Arapova et al., Rus. J. Phys. Chem. , 2009, 83, №8, 1417–1421. [2] B. Lebedev et al., J.Chem.Thermodynamics, 2002, 34, 2093-2103. M. Bubnov et al., Russ.Chem.Bull., Int.Ed., 2011, 60, 440-446. [3] G.L.Pakhomov et al, Rus. J. Nanomaterials and nanostructures, 2010, №2, 39-43. Acknowledgements - We are grateful to the RFBR (grants №№ 13-03-12444, 13-03-97082, 13-03-97070), Russian President Grant supporting Scientific Schools (NSh-1113.2012.3) and Fundamental Research Programm of Presidium of RAS (№ 18) for financial support. We are thankful to O.Kuznetsova and N.Khamaletdinova for NIR-IR spectroscopy experiments, A. Bogom’akov for magnetic measurements. e-mail: bmp@iomc.ras.ru O7 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia DISCOVERY OF CARBON IN “CHELYABINSK” METEORITE BY RAMAN MICRO-MAPPING, S.S. Bukalova, R.R. Aysin, L.A. Leites, V.E. Eremyashev a Scientific and Technical Center on Raman Spectrocopy, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences Vavilova str. 28, Moscow B-334, 119991, RUSSIA. pyroxene Raman intensity, arb. un. Raman intensity, arb. un. 1332 As it is well-known, on Febr. 15 2013 a meteorite has exploded over Russia near Chelyabinsk, giving many fragments, which were gathered and investigated by several groups of Russian geologists and geochemists. They concluded that it was a stony meteorite— a chondrite of the type LL5S4WO. Based on optical reflection, SEM, X-ray diffraction, and TGA methods as well as chemical analysis, mineral content of the meteorite was established. The «Chelyabinsk» meteorite was also investigated in the Scientific and Technical Center on Raman Spectroscopy RAS, using LabRAM an spectrometer (Horiba-Jobin-Yvon) equipped with a microscope×50x (Olympus BX) with 632.8 nm He-Ne laser line excitation. Applying Raman micro-mapping to the freshly cleaved grey surfaces of the meteorite fragments (Fig 1), more than 750 high-quality Raman spectra were registered. Using Horiba-Jobin-Yvon Raman spectra database, the authors identified in the meteorite several minerals, found by other investigators. However, the authors succeeded in detecting several Raman lines belonging to carbon species [1]. These are micro-particles (less than 3 m) of cubic diamond (a very narrow Raman line at 1333 cm-1, FWHM=3.5 cm-1, Fig. 2) and of an sp2-carbon substance (the lines D 1324, G 1598 and 2D 2660 -1, Fig. 3). The latter spectrum nearly coincides with those of natural Karelian shungite and of a sample of industrial glassy carbon. The presence of carbon in the meteorite (0.11%) was confirmed by elemental analysis. Fig. 1. Photographs of two fragments of “Chelyabinsk” meteorite studied. (left) a fragment covered with a black flowed crust; (right) a fragment with a freshly cleaved grey surface 1200 1400 1600 , cm D G 2D -1 Fig. 2. Raman spectrum, registered from a micro-section inside the freshly cleaved meteorite surface, demonstrating presence of cubic diamond. 1000 2000 1 2 3 -1 3000  , cm Fig. 3. Comparison of the Raman spectra of (1) a meteorite micro-spot inside the fresh cleavage, (2) a natural Karelian shungite and (3) a sample of a synthetic glassy carbon. [1] S.S.Bukalov, R.R.Aysin, L.A.Leites, V.E. Eremyashev, Izv. RAS, ser.khim., 2013, 4,1129-1130. Acknowledgements: The authors acknowledge partial financial support from the Russian Foundation for Basic Research (# 13-03-00993) e-mail: buklei.ineos.ac.ru O8 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia IRON(II) CLATHROCHELATES WITH LIGAND-CENTRED REDOX ACTIVITY A. Burdukova, M. Vershinina, N. Pervukhinaa, E. Boguslavskiia, I. Eltsovb, Y. Voloshinc a Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Ave., 630090 Novosibirsk, RUSSIA b Novosibirsk State University, 2 Pirogova str., 630090 Novosibirsk, RUSSIA c Nesmeyanov Institute of Organoelement Compounds RAS, 28 Vavilova str., 119991 Moscow, RUSSIA The macrobicyclic metal tris-dioximates (clathrochelates) are the unique type of the cage coordination compounds that have many unusual properties and possible applications [1]. Recently, it was shown that the cobalt clathrochelates are promising electrocatalysts for very efficient hydrogen production [2 – 4]. However, the rigidity of clathrochelate macrobicyclic frameworks imposes severe limitations on the size of the encapsulated metal ion resulting in the strong stabilization of its particular oxidation state. So, the reversible metal-centred redox reactions of the boron-capped tris-dioximate metal clathrochelates are very limited and mainly characteristic of the cobalt complexes. We extended the redox chemistry of these cage complexes on the ligand-centred processes involving their chelate ribbed fragments. The synthesis of the iron(II) cage complexes with non-innocent ribbed-annulated heterocyclic encapsulating ligands and their redox properties will be discussed. F O N N O B O F O N N Fe2+ N N OO B O H O N H O N H2 N 1. N H2 O N N O O B 2. PbO2 N O O B N N OO B F N B O N N Fe2+ N N OO B N O Cl S S S S S F NH Cl H2N NH2 F O N N O N O O N N Fe2+ O N N Fe2+ N N OO B Zn(dmit)22-, bipy F N H2 F F O N O B O N N Fe2+ N N OO B H N NH N H F F [1] Y.Z. Voloshin, N.A. Kostromina, R. Krämer, Clathrochelates: synthesis, structure and properties, Elsevier: Amsterdam, 2002. [2] O. Pantani, S. Naskar, R. Guillot, P. Millet, E. Anxolabéhère-Mallart, A. Aukauloo, Angew. Chem. Int. Ed. Eng., 2008, 47, 9948-50. [3] Y.Z. Voloshin, A.V. Dolganov, O.A. Varzatskii, Yu.N. Bubnov, Chem. Commun., 2011, 47, 7737-7739. [4] Y.Z. Voloshin, A.S. Belov, A.V. Vologzhanina, G.G. Aleksandrov, A.V. Dolganov, V.V. Novikov, O.A. Varzatskii, Y.N. Bubnov, Dalton Trans., 2012, 41, 6078-6093. Acknowledgements - This study was partly supported by RFBR (grants 13-03-00702 and 12-03-90706). e-mail: lscc@niic.nsc.ru O9 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia IRON(II) COMPLEXES WITH PYRAZOLYLPYRIMIDINES: INTERPLAY BETWEEN SPIN CROSSOVER AND POLYMORPHISM M. Bushueva,b, V. Daletskya, D. Pischura, I. Korol’kova, Yu. Gatilovc, E. Nikolaenkovac and V. Krivopalovc a Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090, Lavrentiev ave, 3, Novosibirsk, RUSSIA. b Novosibirsk State University, 630090, Pirogova str, 2, Novosibirsk, RUSSIA. c N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090, Lavrentiev ave, 9, Novosibirsk, RUSSIA. The spin crossover (SCO) in iron(II) complexes has attracted attention due to its fundamental importance and prospects for applications. The main challenge in this field is the synthesis of complexes undergoing abrupt transition at room or higher temperatures and showing wide bistability domain. Polymorphism in SCO systems is a tool to modulate SCO behavior. Iron(II) complexes with N,N,N-tridentate 2,6-bis(pyrazolyl)pyridines/pyrazines are one of the flexible groups of SCO compounds [1]. We began to study SCO properties of their analogs, i.e., iron(II) complexes with 2,4-bis(1H-pyrazol-1-yl)pyrimidines. A series of high spin complexes have been synthesized. An iron(II) perchlorate complex with 2,4-bis(1H-pyrazol1-yl)-6-methylpyrimidine can be synthesized in the form of two polymorphic modifications. The first one is in the high spin state at room temperature and converts to the low spin state on cooling, while the second modification remains in the high spin state. Thus, 2,4-bis(1Hpyrazol-1-yl)pyrimidines feature rather weak ligand field favoring high spin state either low temperature SCO. To enhance the ligand field and to promote relative stabilization of the low spin state we replaced one of the pyrazol-1-yl groups by the pyridin-2-yl group and synthesized a series of new hybrid ligands, 2-(pyridin-2-yl)-4-(1H-pyrazol-1-yl)pyrimidines. We expected that introducing of pyridinyl group being a stronger σ-donor and π-acceptor than pyrazole should stabilize the low spin state and shift the transition to higher temperatures. Magnetic data on iron(II) complexes with 2-(pyridin-2-yl)-4-(1H-pyrazol-1-yl)pyrimidines confirmed this hypothesis. These compounds are in the low spin state at room temperature and undergo a transition to the high spin state above room temperature. An iron(II) tetrafluoroborate complex with 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2yl)-6-methylpyrimidine is of special interest. It shows unusually complicated interplay between spin crossover behavior and polymorphism. Depending on the experimental conditions, the starting low spin complex can be converted into one of three low spin phases showing different spin crossover regimes. Two of them display gradual spin transition centered around 320 K. The third phase show reproducible SCO behavior with abrupt transitions at 490 and 360 K for the heating and cooling modes, respectively. Thus, an unprecedented hysteresis loop of 130 K was observed. [1] M. A. Halcrow, Coord. Chem. Rev., 2009, 253, 2493-2514. Acknowledgements - The work was financially supported by Russian Foundation for Basic Research (Project 12-03-31032 mol_a). e-mail: bushuev@niic.nsc.ru, dalvas@niic.nsc.ru, denispischur@ngs.ru, krivic@nioch.nsc.ru O10 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FIRST EXAMPLE OF COEXISTENCE OF THE MAGNETIC ORDERING, PRESUMABLE MAGNETOELECTRIC EFFECT AND SPIN CROSSOVER IN DENDRIMERIC IRON(III) COMPLEX N. Domrachevaa, A. Pyataevb, V. Vorobevaa, E. Zuevac a Zavoisky Kazan Physical-Technical Institute of Russian Academy of Science, 420029, Sibirsky Tract, 10/7, Kazan, RUSSIA b Kazan Federal University, 420008, Kremlyovskaya St., 18, Kazan, RUSSIA c Kazan State Technological Institute, 420015, K. Marx Street, 68, Kazan, RUSSIA The unusual magnetic behavior of the first dendritic Fe3+ complex [1] with general formula [Fe(L)2]+Cl¯ H2O based on a branched Schiff base has been investigated by electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. EPR display that complex consists of the three types of magnetically active iron centers: one S = 1/2 low-spin (LS) and two S = 5/2 high-spin (HS) centers with strong low-symmetry and weak distorted octahedral crystal fields. Calculation of the g-tensor component (gx,y = 2.21, gz = 1.935) of the LS Fe3+ centers has shown that (dxz,dyz)4(dxy)1 state is the ground. Analysis of the magnetic behavior reflected by I versus T (where I is the EPR lines integrated intensity of the whole spectrum which is proportional to the static paramagnetic susceptibility) demonstrates that dendritic Fe3+ complex has sufficiently different behavior in three temperature intervals. The first (4.250 K) interval corresponds to the intermolecular exchange interactions between LS-LS, LSHS and HS-HS centers coupled antiferromagnetically by means of water molecules and Cl counterions. The appearance of the presumable magnetoelectric effect is registered in the second (50-200 K) temperature interval, whereas a spin transition process between LS and HS centers occurs in the third (200-330 K) one. Simulation of the EPR spectra allowed us to trace the dynamics of changing the number of HS centers with respect to LS during a spin crossover. It has been shown that spin transition process is characterized by the following enthalpy H = 3.46 kJ/mol and entropy S = 58.8 J·K-1/mol values. The simultaneous coexistence of the magnetic ordering, presumable magnetoelectric effect and spin crossover in one and the same material has been revealed for the first time. The Mössbauer spectroscopy data completely confirm the EPR results. DFT calculations demonstrate the coordination sphere structure of the compound. [1] M. Gruzdev, N. Domracheva, U. Chervonova, A. Kolker, A. Golubeva J. Coord. Chem., 2012, 65, 18121820. Acknowledgements - We gratefully acknowledge the financial support for this work by RAS Presidium program No. 24 and in part by the RFBR, project No. 11-03-01028. e-mail: domracheva@mail.knc.ru, 151eu@mail.ru, vvalerika@gmail.com, zueva_ekaterina@mail.ru O11 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia UNCONVENTIONAL MECHANISM OF Pd COMPLEXES OXIDATION BY AQUEOUS ACIDIC SOLUTION OF H2O2: KINETIC AND DFT STUDY E. Evstigneeva Lomonosov Moscow University of Fine Chemical Technologies, 119571, prosp. Vernadskogo, 86, Moscow, RUSSIA. Hydrogen peroxide is an environmentally friendly and cheap oxidant suitable for usage in processes catalyzed by transition metal complexes [1]. Its practical application is limited by unproductive H2O2 decomposition and by kinetically unfavored oxidation of reduced form of Pd in Wacker-type reactions. It has been stated that in dilute hydrogen chloride both rate and selectivity depend on the acid/H2O2 ratio [2]. Acid addition accelerates electrophilic oxidations by H2O2 what is representing in a kinetic equation containing a third order term with acid concentration [1]: r  k2 [ H 2O2 ][ Nu ]  k3 [ H 2O2 ][ Nu ][ HA] (1) This term is explained by protonation of H2O2 (2) which leads to highly electrophilic hydroperoxonium ion H3O2+ formation [1]: K H3O2+ + H2O, K = 10-3 at 298 H2O2 + H3O+ (2) + Hydroperoxonium ion H3O2 can act as oxidizing specie under mild conditions and can be regarded as hydrated hydroxyl cation HO+. Earlier [3] selective oxidation of terminally substituted allylic complexes into linear allyl derivatives (3) was studied. For complex with R = MeCH(OH) kinetic equation (4) of fourth total order was received. [(R- 3-C3H4)PdCl2]- + H2O2 + HCl → RCH=CHCH2OH + Clr  k obs. [ H 2O2 ][ H  ][ Cl  ][ 3 ] (3) (4) DFT study (approximation PCM-B3LYP/LANL2DZ(Pd)+6-31+G*) supposed + unconventional mechanism of reaction (3). It includes direct addition of H3O2 to the central atom of complex anion [(R- 3-C3H4)PdIICl2]- with formation of neutral intermediate ( 3RC3H4)PdIV(OH)Cl2, which isomerizes into thermodynamically more stable 1-allylic complex having unconventional disphenoid structure. At the rate-determining step external nucleophilic attack of Cl- onto carbon atom in ( 1-RC3H4)PdIV(OH)Cl2 to form allylchloride and Pd(II) complex occurs. So the first order in chloride ions agrees with change of hapticity of 3-allylic complex. The mechanism was proved by IRC calculations and by single imaginary frequency found for each transition state. [1] Catalytic oxidations with hydrogen peroxide as oxidant / Strukul G., ed. / Kluwer, Dordrecht - 1993, 300 p. [2] T. Antonsson, S. Hansson and C. Moberg, Acta Chem. Scand. B, 1985, 39, 593-596 [3] E.M. Evstigneeva, S.M. Kalabin and A.P. Belov, Russ. J. Coord. Chem., 1995, 21, 49-53 [4] H. Shi, Y. Wang and Z. Zhang, J. Mol. Cat. A: Chemical, 2006, 258 (1-2), 35-45 Acknowledgements - Author appreciates Russian Foundation for Basic Research for financial support (project № 11-03-00662- ). e-mail: eme2003@list.ru O12 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF ANTITUMOR HETEROCYCLE-CONTAINING ALLOCOLCHICINOIDS A. Fedorova, N. Sitnikova, Yu. Voitovich a, E. Knyazeva a, J. Velder b, and H.-G. Schmalz b a N.I. Lobachevsky Nizhny Novgorod State University, Organic Chemistry Department, 603950, Gagarin avenue 23, Nizhny Novgorod, RUSSIA b Universität zu Köln, Department für Chemie, Greinstr. 4, Köln, 50939, GERMANY A range of indole- and furane-containing allocolchicinoids was synthesized using the methods of metallocomplex catalysis: MeO X MeO MeO MeO MeO MeO X MeO MeO MeO MeO MeO MeO N N X X O N R MeO MeO X MeO MeO N X MeO MeO X = OH, N3, NH2, NHAc N Several from synthesized compounds manifest antitumor activity at nanomalar or even at subnanomolar concentration range [1], along with particularly low unspecific toxicity. [1] N.S. Sitnikov, J. Velder, L. Abodo, N. Cuvelier, J. Neudorlf, A. Prokop, G. Krause, A. Yu. Fedorov, H.-G. Schmalz, Chem. Eur. J., 2012, 18, 12096-12102 Acknowledgements - this work was supported by the DAAD Program (A/08/79551), Russian Federal Target Program (16.740.11.0476) and Russian Foundation for Basic Research (12-03-00214-a). e-mail: afnn@rambler.ru, nikolaj-sitnikov@ya.ru, schmalz@uni-koeln.de O13 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia REGIO/STEREOSELECTIVE CATALYTIC NORBORNADIENE ALLYLATION BY Ni AND Pd COMPLEXES. NEW SINTHETIC POSSIBILITIES AND MECHANISM. V. Flid, R. Shamsiev M.V. Lomonosov Moscow State University of Fine Chemical Technologies Vernadsky Prosp., 86, Moscow, 119571 Russia The report comprises results concerning unusual direction of transition metal allyl complexes, that is redox disproportionation of allyl ligands. The share of disproportionation depends on the effective positive charge (from +0,4 up to +0,8) on metal and the substrate nature. CO2 O + O (1) O O + M Cl + + C3H6 (2) Cl (3) C9H16 + C9H14 1. M – Ni, Pd; 2. M – Fe, Co, Ni, Rh, Pd, Pt; 3. M – Ni Nonconventional catalytic allylation of norbornenes and norbornadiene (NBD) by allylacetates and allylcarbonates is the unique synthetic method allowing to introduce in NBD of structure methylen-, vinyland methylenecyclobutane fragments. + OCR M(0) + + + RCOOH (4) O New catalysts for the unconventional NBD allylation by allyl acetate, allyl formiate, methylallyl carbonate and diallyl carbonate (reaction 4) were investigated based on palladium phosphine systems: Pd(dba)2+2PPh3, Pd(OAc)2+2PPh3, PdCl2(PPh3)2, [(C3H5)Pd]NO3+2PPh3. Phosphite nickel complexes show high catalytic activity and also high regio- and stereoselectivity only in the complete absence of oxygen. Phosphine palladium complexes carry out catalytic process with high parameters in normal conditions. On the basis of X-ray photoelectron and 1H-, 13C-, 31P-NMR spectroscopy and kinetic data it was shown, that nickel and palladium have qualitative analogies in this reaction. The ratio of stereoisomers and the number of catalytic cycles depends on the metal – ligands ratio. The mechanism of reaction proceeding with the participation of both metals was offered. β-Hydride transfer with participation different metals, allylic and NBD fragments was confirmed by isotopic methods. Acknowledgements: RFBR supported this work, grant 11-03-00662. E-mail: vitaly-flid@yandex.ru O14 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia NEW CATALYTIC SYSYEMS FOR ORGANOMETALLIC MEDIATED RADICAL POLYMERIZATION OF VINYL NOMERS D. F. Grishin Lobachevsky State University of Nizhny Novgorod, 23 Gagarina Prospect, Nizhny Novgorod, 603950 RUSSIA Organometallic mediated radical polymerization has become one of the most important and effective methods of polymer synthesis in recent years. The use of organometallic compounds for precise polymer synthesis is perspective division in modern polymer chemistry. It allows not only to control the polymerization kinetics and molecularweight parameters of macromolecules but offers scope for effective solutions of problems of macromolecular design owing to an opportunity to synthesize graft and block copolymers as well as macromolecular nanostructures. It has been shown in our laboratory that the complexes of ruthenium, nickel, cobalt, iron, tin and some other metals with different ligands does not only initiate radical homo- and copolymerization of styrene, vinyl chloride, acrylonitrile, methyl methacrylate, butyl acrylate and some other vinyl monomers but have a significant impact on the propagation stage of the polymer chain. A particular attention has been paid to the application of complexes of transition metals with variable valence in processes of macromolecule synthesis by Atom Transfer Radical Polymerization as the most effective approach to the carrying out of polymerization under “living” chain conditions. It has been shown that a series of organometallic compounds are able to control the polymer chain growth through the mechanism of Reverse Organometallic Radical Polymerization exerting substantial influence on the molecular-weight characteristics of homo- and copolymers as well as their composition and the microstructure. In such processes metalocomplexes play a role of a reversible spin trap for polymer radicals, regulating their concentration and preventing from the bimolecular termination like stable nitroxyl radicals. New original agents based on sterically hindered quinones and catecholate complexes of IV group elements are offered for the controlled synthesis of macromolecules via the mechanism of Quinone Transfer Radical Polymerization. The influence of investigated organometallic complexes especially the electronic structure of the metal atom and the ligand environment on the mechanism of polymerization as well as molecular weight parameters, composition and some properties of obtained homoand copolymers were estimated. Acknowledgements - This work was supported Russian Ministry of Education and Science (“Federal target program of scientific and scientific-pedagogical personnel of innovation of Russia on 2009-2013”) and Russian Foundation of Basic Research (pr. 11-03-00074). e-mail: grishin@ichem.unn.ru O15 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia RADICAL REACTIONS OF RUTHENIUM CARBORANE COMPLEXES: HALOGEN EXCHANGE AND CATALYSIS OF RADICAL POLYMERIZATION Ivan D. Grishina, Elena S. Turminaa, Dmitry I. D’yachihinb, Igor T.Chizhevskyb and Dmitry F. Grishina a Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina prosp, 23/5, Nizhny Novgorod, RUSSIA. b A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilov str, 28, Moscow, RUSSIA. Ruthenium compounds are known as perfect catalysts of radical reactions, such as Kharasch addition and controlled radical polymerization via ATRP mechanism. Among them ruthenium carborane complexes are of a special interest due to their high stability and efficiency. Dicarbollide ligand is capable to stabilize metal centres in high oxidation state due to double negative charge and high degree of electron delocalization. Here we report the radical reactions of ruthenium carborane complexes with chelate diphosphine ligands, namely halogen exchange and catalysis of radical polymerization. Reactions of chloride-containing paramagnetic ruthenium carborane complexes with excess of carbon tetrabromide in benzene or toluene give corresponding bromine-containing compounds with high yields (60-90%) in 4 hours. The full conversion of initial compounds was confirmed by HPLC and MALDI MS experiments. Halogen exchange reaction is a more convenient way of obtaining of bromine containing ruthenacarboranes in comparison with conventional way through exo-nido -> closo rearrangement and further thermolysis [1-2]. (CH2)n (CH2)n PPh2 Ph2P Ru PPh2 Ph2P Cl Ru Br CBr4 n=2-5 The obtained bromine complexes as well as their chlorine containing precursors were investigated in catalysis or controlled radical polymerization of methacrylates and styrene. The proposed catalysts allow to obtain polymers with low polydispersity (Mw/Mn=1.1-1.4) and desired molecular weight. The linear increase of molecular weight with conversion and successful synthesis ob block-copolymers confirms controlled manner of polymerization. Our investigations show that amine additives significantly accelerate controlled polymerization of MMA in the presence of ruthenacarboranes. Polydispersity of the formed polymers remains very narrow (<1.2) in spite of little decrease of control over polymerization. It was shown, that presence of amine additives allows to decrease catalyst concentration while the process remains controlled. [1] I.Grishin, D.D’yachihin, E.Turmina et. al.. J. Organomet.Chem, 2012, 721-722, 113-118. [2] I.Grishin D.D’yachihin, A.Piskunov et. al. Inorg. Chem, 2011, 50, 7574-7585. Acknowledgements - This work was supported by Grant of President of Russian Federation (MK391.2013.3) and Russian Foundation for Basic Researches (Proj. 12-03-00102 and 12-03-31148). e-mail: grishin_i@ichem.unn.ru, chizbor@ineos.ac.ru O16 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia RATIONALIZATION OF SOLVATION AND STABILIZATION OF PALLADIUM NANOARTICLES IN IMIDAZOLIUM- AND PHOSPHONIUM-BASED IONIC LIQUIDS S. Katsyubaa, E. Zverevaa, N. Yanb, X. Yuanb, V. Ermolaeva, V. Miluykova, O. Sinyashina and P. Dysonb a A. E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Centre of Russian Academy of Sciences, 420088, Arbuzova str, 8, Kazan, RUSSIA. b Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des Sciences et Ingénierie Chimiques, EPFL – BCH, CH–1015 Lausanne, SWITZERLAND. Metal nanoparticles (M-NPs) attract interest across diverse areas of science. Small M-NPs are only kinetically stable and combine to form thermodynamically favoured larger metal particles via agglomeration. Ionic liquids (ILs) can be used to generate and stabilise metallic NPs in situ. The required stabilization is provided through the formation of an ion layer around the M-NPs. The nature of this layer and hence, the mode of stabilization of M-NPs in ILs, is still a matter of debate. We applied the combined DFT-vibrational spectroscopy approach to determine the interactions of ionic components of various ILs based on the 1alkyl-3-methylimidazolium [Cnmim], 1-(2'-hydroxylethyl)-3-methylimidazolium [C2OHmim] and the tetraalkylphosphonium cations with Pd NPs immersed in the ILs. According to the computations, Pdn (n=5 - 21) clusters, taken as models of Pd NP, interact more strongly with the anions than with the cations [1,2]. The following order was obtained for interaction energies between a Pdn cluster and various anions: [TFA] (trifluoroacetate) > [BF4] > [OTf] > [PF6]  [Tf2N]. The IR spectra suggest that both the anions and cations in the ILs interact with the Pd-NP surface. In agreement with the above findings, the influence of both the cationic and anionic components of the ILs on the properties of Pd NPs, formed and stabilized in situ, were established experimentally [2]. Indeed the anions, which exhibit the strongest interaction with the Pd5 cluster, resulted in the lowest extent of Pd NP formation whereas the anions with weakest interactions provided the highest percentage of Pd NPs. A presence of the latter weakly-interacting anions in IL results in the formation of the largest-size NPs, while the smallest-size NPs are formed in ILs containing strongly interacting anions. [C2OHmim]-based ILs allows the formation of the smaller NPs than [C2mim]-based ILs. This finding, as well as the formation of the largest NPs in tetraalkylphosphonium-based ILs, agrees with the order of the cluster-cation interactions: [C2OHmim] > [C2mim] > tetraalkylphosphonium. The energy of the interaction of the IL components with Pdn clusters is shown to be smaller than the energy of addition of a Pd atom to the cluster. Stronger Pd-Pd interactions in comparison to the interactions of the palladium cluster with the IL suggest kinetic stabilisation of Pd-NPs in the ILs rather than thermodynamic stabilisation. This feature could explain why Pd-NP catalyst reservoirs that react to form catalytically active mononuclear palladium species in cross coupling reactions are particularly active in ILs. [1] S.A.Katsyuba, E.E.Zvereva, N.Yan, X.Yuan, Y.Kou and P.J.Dyson. Chem.Phys.Chem. 2012, 13, 1781-1790. [2] X.Yuan, N.Yan, S.A.Katsyuba, E.E.Zvereva, Y.Kou and P.J.Dyson. Phys.Chem.Chem.Phys., 2012, 14, 60266033 Acknowledgements - Financial supports from the Switzerland-Russia S&T Cooperation Program and the Russian Foundation for Basic Research (grant 12-03-31214_mol-a) are gratefully acknowledged. e-mail: katsyuba@iopc.ru O17 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND PHYSICO-CHEMICAL STUDIES OF SOME SEVEN AND TEN COORDINATED COMPLEXES OF LANTHANIDES(III) DERIVED FROM SEMICARBAZONE CONTAING HETEROCYCLIC RING Sanjay Dutt Kaushik Department of Chemistry, Lajpat Rai Postgraduate College, Sahibabad-201005 (Ghaziabad), INDIA. The structural chemistry of the lanthanide (III) compounds has recently undergone considerable development and a wide variety of coordination numbers and geometries have been observed. The coordination numbers exhibited by the tripositive lanthanide ions usually vary from 6 to 10. However, other examples of lanthanide (III) complexes with more than 10coordination number have also been reported in the literature. In the present studies the effect of quinoline N-oxide (QNO) on the stereochemistry of the coordination compounds of trivalent lanthanides derived from 4[N-(2’,4’-dimethylbenzalidene)amino]antipyrine semicarbazone (DMBAAPS) is reported. The general composition of these coordination compounds is LnX3.n (DMBAAPS).QNO (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy or Ho ; X = NO3, n = 1, X = ClO4 or NCS, n = 2). All these compounds were characterized by elemental analysis, molar mass, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies reveal that the DMBBAAPS acts as a neutral tridentate (N,N,O), while QNO is coordinated to the central metal ion via its lone oxygen atom. In nitrato complexes, the nitrates ions are bicovalently bonded, while thiocyanate is coordinated through hard N-atom. Perchlorato ions are not participating in coordination and are present outside the coordination sphere. From electronic spectral data, nephelauxetic effect (β), covalence factor (b1/2), Sinha parameter ( %) and the covalence angular overlap parameter ( ) has been calculated. Antibacterial properties of these compounds were also studied. Thermal studies of these compounds were studied by thermogravimetric analysis. The present studies reveal that the coordination number of lanthanide(III) in the present compounds is either 7 or 10 depending on the nature of anions. e-mail: sdkaushik11@gmail.com O18 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia REMARKABLE INSERTION OF ELECTROPHILIC PHOSPHINIDENE COMPLEXES INTO CARBON-HALOGEN BONDS Arif Ali Khan University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, Dwarka, Sec.16-C, New Delhi – 110078, INDIA. Phosphinidenes are phosphorus analogue of carbenes. Phosphinidene tungsten pentacarbonyl complexes could be generated in-situ only which are extremely unstable and highly reactive. A remarkable insertion of these phosphinidene complexes into carbon-halogen bonds was observed. These intermediates could be trapped easily in presence of various reagents containing π-systems to afford a number of P-heterocycles1. A number of compounds are known to give phosphinidene intermediates but 2H-azaphosphirene tungsten pentacarbonyl complex (1) is the most stable precursor for the in-situ generation of terminal phosphinidene complexes (2), via thermal decomposition of 1, which can be trapped via [2+1] cycloaddition reactions1 or with C-X bond systems leading to selective insertion reactions2-5 – all reactions and their manipulations were carried out under strict anhydrous conditions and were monitored by 31P NMR spectroscopy. All products were characterized by NMR spectroscopy and by single-crystal X-ray crystallography. [1] A. A. Khan, C. Neumann, C. Wismach, P. G. Jones and R. Streubel. J. Organomet. Chem. 2003,682, 212217. [2] A. A. Khan, C. Wismach, P. G. Jones and R. Streubel, Dalton Trans., 2003, 2483. [3] A. A. Khan, C. Wismach, P. G. Jones and R. Streubel, Chem. Commun. 2003, 2892. [4] A. Özbolat, A. A. Khan, G. von Frantzius, M. Nieger, and R. Streubel, Angew. Chem., Int. Ed. Engl., 2007, 46, 2104. [5] A. A. Khan, G. Schnakenburg, and R. Streubel, unpublished work. Acknowledgements – Author is thankful to Prof. R. Streubel (Institute of Inorganic Chemistry, University of Bonn, Bonn, Germany) for research collaboration and DFG-Germany for funding. Author is also thankful to CSIR- New Delhi (India) for granting permission for this collaboration. e-mail: khanaarif@hotmail.com O19 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia VIBRATIONAL SPECTRA AND ELECTRONIC STRUCTURE OF 1GERMATRANOL, 1,1-QUASIGERMATRANEDIOL, AND 1,1,1HYPOGERMATRANETRIOL (HO)4-n Ge(OCH2CH2)nNR3-n (R=H; n=1-3) T. Kochinaa, I. Ignatyevb, M.Voronkovc a Institute of Silicate Chemistry of Russian Academy of Sciences, 199034, Adm. Makarova emb., 2, Saint-Petersburg, RUSSIA. b Saint Petersburg State University, 198504, University Ave, 26, Petrodvorets, Saint-Petersburg, RUSSIA. c Favorsky Institute of Chemistry SB RAS, 664033, Favorsky St., 1, Irkutsk, RUSSIA. IR spectra of 1-germatranol, 1,1-quasigermatranol, and 1,1,1-hypogermatranol with general formula (HO)4-nGe(OCH2CH2)nNR3-n (R=H; n=1-3) are recorded. Equilibrium structures and vibrational spectra of monomeric and centrosymmetric dimeric species of these compounds are predicted by the B3LYP/aug-cc-pVDZ method. The X-ray diffraction study [1] indicates that the crystal structure of 1-germatranol consists of hydrogen-bonded dimers [HOGe(OCH2CH2)3N]2 in which the hydroxyl group proton of one monomer is bound to endocyclic oxygen of another. The crystal structure of 1,1-quasigermatranol is also built from dimers, however the pattern of hydrogen-bonding in these dimers is diffent since only hydroxyl groups are involved in this bonding: one OH group in each molecule acts as a proton donor and another as an acceptor. The analysis of experimental spectra based on theoretical predictions of the vibrational spectra of dimeric species of these compounds confirms the character of hydrogen-bonding in these compounds. The structure of 1,1,1-hypogermatranol is not known and the comparison of experimental and theoretical spectra indicate that the crystal structure of this compound cannot be satisfactorily described in the dimeric model. The persistent difference between the length of the transannular Ge…N bond length in the gas and solid phases manifests itself in the comparison of theoretical and experimental spectra of all species studied. In this work this difference was compensated by scaling of theoretical GeN force constants. [1] M.G. Voronkov, A.A. Korlyukov, E.A. Zelbst, S.P. Knyazev, I.M. Vasilyev, E.A. Chernyshev, M.Yu. Antipin, J. Struct. Chem. 51 (2010) 719-724. e-mail: t-kochina@mail.ru, radiochem@yandex.ru, voronkov@irioch.irk.ru O20 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia DIAZADIPHOSPHAPENTALENE: AROMATIC MOLECULE WITH TWOCOORDINATE AND FORMALLY TWO-VALENT PHOSPHORUS A.N. Korneva, V.V. Sushev, and J.S. Panova, a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Reduction of dichlorodiazaphosphalene 1 [1] results in formation of diazadiphosphapentalene 2. This is diamagnetic compound showing single resonance in 31P NMR spectrum at 177.0 ppm. The bond distance between the two carbon atoms in the PCCN fragment (1.335(7) Å) is corresponded to the normal double C=C bond in alkenes. The C–P, P–N, N–N and N–C bond lengths lie in the range, typical Cl for 1,2,3-diazaphospholes. It is P P P + 2e N N N important to note that the N N N -2Cl shortest distances between the P P P 2 1 Cl phosphorus atoms of adjacent molecules in crystal (4.180 Å) exceed the sum of van der Waals radii (3.60Å). Calculated NICS(0) of –11.44 is compatible with an aromatic character of the cyclic C2N2P moieties. Interestingly, the equimolar mixture of 1 and 2 gives new easily dissociated compound 3 which after reaction with Cl GeCl2 forms structurally 2+ characterized complex 4. It is P P N N important to highlight that the P N N P 2GeCl3 positively 2 GeCl2 charged diazaP N N diphosphapentalene units can P N P P N effectively bind to each other 4 not only by P-P single bond. Cl 3 Formation of staked 18-e dication may be explained by the concept of stacked-ring aromaticity assuming throughspace delocalization of π-electrons. Activity of 2 in coordination bond formation is very high that may be explained rather by unusual mechanism of complexation. While M the lone pair of sp2 phosphorus is poor P P available, the 10e system may submit N N + M+ another two electrons via phosphorus atom, + N N P taking away one electron from neighboring P phosphorus. Complexes of 2 with HgCl2 and SnCl2 demonstrate supramolecular organization dependent on preparation method. The molecule 2 possesses reducing activity, converting easily Ph2PCl to Ph4P2 and PhPCl2 to (PhP)5. Reaction with Ph3CCl gives the P,P’-addition product {Ph3C-PNNP-Cl}. One equivalent of 3,6-Di-tBu-o-quinone interacts to one phosphorus atom of 2 to form hypervalent (four-coordinate) phosphorus(III) compound. [1] A. N. Kornev, O. Y. Gorak, et al, Z. Anorg. Allg. Chem. 2012 638, (7-8), 1173–1178. Acknowledgements - This work was supported by The Russian President’s program “Leading Scientific Schools” (No. 7065.2010.3) and RFBR regional grant No 13-03-97096. e-mail: akornev@iomc.ras.ru O21 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia SYNTHETIC APPLICATION AND CATALYTIC ACTIVITY OF CATIONIC (ARENE)METALLACARBORANES D. A. Loginova, M. M. Vinogradov, A. O. Belova and A. R. Kudinov a A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow GSP-1, Russian Federation. (Arene)metallacarboranes are perspective compounds as a synthons of the CarbM fragments owing to high substitutional lability of the arene ligand. In particular, we shown that photochemical replacement of benzene in the iron complex 1 by other ligands is an effective method for the direct preparation of the hard to get metallacarboranes, namely, unsymmetrical bis(carborane) complexes and triple-decker compounds. The (benzene)rhoda- and iridacarboranes 2 and 3 catalyze the coupling of benzoic acid with alkynes. In the case of rhodium, naphthalenes were isolated as the major products. In contrast, the coupling catalyzed by iridium complex 3 results in isocoumarin derivatives exclusively. These and other similar (arene)metallacarboranes will be discussed, along with their reactivity and structures. Acknowledgements - This work was supported by the Presidium of Russian Academy of Sciences (program P8). e-mail: dloginov@ineos.ac.ru O22 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia TARGRTED ELECTROSYNTHESIS IN COORDINATION ENVIRONMENT OF CHIRAL Ni(II) COMPLEXES OF α-AMINO ACID SCHIFF BASE: A CONVINIENT ROUTE TO α-AMINO ACID FUNCTIONALIZATION T. Magdesievaa, O. Levitskiya, A. Ambartsumyanb, K. Kochetkovb a Dept. of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russia b Nesmeyanov Organoelement Institute, Vavilov str., 28, Moscow, Russia Metal complexes with chiral ligands create an efficient asymmetric environment around the metal center to afford the high-level induction of enantioselectivity. This approach is widely used for various types of stereoselective synthesis. However, an involvement of a substrate in the asymmetric metal coordination environment allows not only providing asymmetric induction but also opens a possibility to perform electrochemically induced stereoselective reactions, thus broadening a scope of available reaction routes. Aforementioned novel approach was used for developing of practical and highly efficient routes to various types of α-amino acid derivatives. Electrochemically induced reactions in coordination environment of three different chiral Ni(II) complexes of α-amino acid Schiffbase (glycine, alanine, dehydroalanine) were elaborated. Various types of chemical transformations will be considered, including oxidative or reductive activation of starting complexes as well as their in situ reactions with electrochemically generated species. The consideration of possible sites of cathodic and anodic activation in Ni(II) complexes was performed in the context of their electrochemical behavior and quantum-chemical DFT calculations of their frontier orbitals. Varying the type of activation (anodic or cathodic), different types of Ni(II) binuclear complexes can be obtained. Further electrochemical reduction of new dimers allows obtaining chiral mixed-valence species which might be of interest for catalytic applications. The reactions of glycine and alanine Ni(II) complexes with electrochemically generated base open a route to various condensation reactions. Since some of them have been performed earlier using common bases [1], the comparison of stereochemical result of chemical and electrochemical transformations might be of interest. The elaborated approach to enantiopure β-hydroxy α-amino-acids using galvanostatic electrolysis of Ni(II) complexes of glycine Schiff-base in alcohols in one-compartment cell in the presence of KOH constitutes a convenient and more practical alternative to common aldol reaction with aldehydes [1]. The relative and absolute configurations of the products isolated using column chromatography were determined from NMR and CD spectra. The modified Ni(II)-Schiff base complexes can be easily decomposed using HCl in methanol yielding various amino acids derivatives. [1]. Y.N. Belokon, K.A. Kochetkov, N.S. Ikonnikov, T.V. Strelkova,S.R. Harutyunyan, A.S. Saghiyan,Tetrahedron: Asymmetry 12 (2001) 481 Acknowledgement: This work was supported by Russian Foundation of Basic Research (Project № 011-0300220) e-mail: tvm@org.chem.msu.ru O23 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia COEXISTENCE OF FERROMAGNETIZM AND CONDUCTIVITY IN IRON MIXED-VALENT ANILATO-BRIDGED NETWORKS. FIRST EVIDENCE OF DOUBLE-EXCHANGE INTERACTION N. S. Ovanesyana, Z. K. Nikitinaa, G. V. Shilova, S. M. Aldoshina, Y. Lib, M. Gruselleb, C. Trainc a Institute of Problems of Chemical Physics, 1, Semenov av., Chernogolovka, 142432, Russia b Université P&M Curie, 4 place Jussieu, 75252 Paris Cedex 05, France c Université Joseph Fourier, B. P. 53, 38041 Grenoble Cedex 9, France Synthesizing and studying the physical properties of multifunctional molecule-based materials is currently blossoming [1]. Our objective is the systematic study of the effects related to the coexistence within the one material of several physical properties and/or to the resulting cross-effects [2]. Our next pathway consisted in replacing the oxalate ligand by non-innocent bridge. Metal compounds containing (DHBQ)2-, choranilate (CA)2- etc., as bis-bidendantate ligands having delocalized π-system are attractive for constracting new molecule-based magnets. Recently, both bimetallic (NBu4)2[MFe(CA)3], M=Mn-Cu, and monometallic (H3O)2(phz)3[M2(CA)3], M=Mn, Fe, compounds with extended networks were syntesized [3, 4]. Here we report a characterization of a new family of monometallic compounds with TBA counter cation, (NBu4)[M2(C6Cl2O4)3], M=Mn, Fe, Cu. They possess a stack of layered [M2(C6Cl2O4)3]2anionic networks separated by a double (NBu4)+ cationic layer. A charge delocalized Fe2.5+ state related to the rapid electronic exchange has been evidenced by the Mossbauer spectroscopy leading to a ferromagnetic long-range order of iron magnetic moments following the double exchange mechanism. In contrast to many molecular magnets, usually belonging to the category of insulators, the double-exchange interaction between the metal centers favors a semiconducting behavior with low activation energy. Thus, a functional molecular material combining ferromagnetism and electrical conductivity within the same sub-lattice has been obtained for the first time. 1000 R, ohm*m (NBu4)2Fe2(C6Cl2O4)3 H = 0T,  = 0.149 eV 100 H = 1T,  = 0.147 eV H = 9T,  = 0.146 eV 0T(350) = 5.910-4 ohm-1 cm-1 9T(350) = 8.410-4 ohm-1 cm-1 10 3,0 3,5 4,0 4,5 5,0 5,5 1000/T [1] R. Clement, S. Decurtins, M. Gruselle, C. Train, Monatsh. Chem. 2003, 134, 117. [2] C. Train, R. Gheorghe, V. Krstic, L. M. Chamoreau, N. Ovanesyan, G. Rikken, M. Gruselle, M. Verdaguer, Nature Mater. 2008, 7, 729. [3] Z.K. Nikitina, N.S. Ovanesyan, V.D. Makhaev et al., Doklady Chemistry, 2011, 437, 129‐ 132. [4] G.V. Shilov, Z.K. Nikitina, N.S. Ovanesyan et al., Russian Chemical Bulletin, 2011, 60, 1209-1219. Acknowledgements – Supported by CNRS – RFBR joint project #91054 e-mail: ovanesyan@icp.ac.ru O24 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia METALLOCENE AND BIS(ARENE) COMPLEXES OF TRANSITION METALS WITH 1,2,5-CHALCOGENADIAZOLE RADICAL ANIONS — A NEW APPROACH TO HETEROSPIN SYSTEMS Nikolay A. Pushkarevskya, Nikolay A. Semenovb, Sergey N. Konchenkoa and Andrey V. Zibarevb a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentiev Ave., 3, Novosibirsk 630090, Russia b Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentiev Ave. 9, Novosibirsk 630090, Russia Chalcogenadiazoles represent an important type of main group element compounds, subclass of a large family of chalcogen-nitrogen π-heterocycles. An interesting feature is their positive electronic affinity, which gives them a possibility to turn to stable radical anions (RAs) upon reduction. This property can be efficiently used for the synthesis of crystalline phases based on combinations of the RAs with suitable radical cations; such heterospin salts may possess different types of magnetic ordering. We are investigating an approach of using reductive sandwich metal complexes, such as MCp*2 and M(Arene)2, as both the reducing agents and sources of radical cations. 3,4-Dicyano-1,2,5-chalcogenadiazoles (S, Se) were shown to react with CrCp*2 to give crystalline salts (scheme A), which are heterospin, S1 = 3/2 and S2 = 1/2, systems experimentally featuring antiferromagnetic exchange interactions. Their Te congener has a prominent propensity to Te···N interactions to form coordination bonding, which precludes the formation of separate radical anions in the crystalline state. To achieve ferromagnetic ordering, the spin canting model of interacting spins can be implemented, which requires spin-orbit coupling at heavier metal atoms (the DzyaloshiskyMorya mechanism). To this end, we involved MAr2 complexes (Ar = toluene, mesitylene; M = Cr, Mo) as reducing agents. Compounds CrAr2 do not interact with the heterocycles 1 and 2. Reactions take place with the heterocycles possessing larger electron affinity (3—5, scheme B), to give heterospin radical-ion species. Their EPR spectra show broad signals of radical cations and multiplets corresponding to RA. Heterocycle redox properties depend on the structure; the strongest acceptor 5 can be reduced with decamethylferrocene to give heterospin radical-ion salt. Acknowledgements: The authors are grateful to the Russian Foundation for Basic Research (projects 12-0331530, 12-03-31759 and 13-01-01088), Presidium of the Russian Academy of Sciences (project 8.14), Siberian Branch of the Russian Academy of Sciences (project 13), and Federal Target Program “Kadry” (Contract 8631) for financial support. e-mail: nikolay@niic.nsc.ru O25 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia CHARACTERIZATION AND ANTIBACTERIAL PROPERTIES OF DIOXOMOLYBDENUM(VI) COMPLEXES WITH SYMMETRICAL TETRADENTATE SCHIFF BASE Devendra Pratap Rao Department of Chemistry, D.A-V. P.G. College, Kanpur 208001, Uttar Pradesh, INDIA Synthesis of five new dioxomolybdenum(VI) complexes having formula [MoO2(mac)](acac)2, with a Schiff base , derived from condensation of furil with 2,3diamino-5-bromopyridine and their cyclization with β-diketones are reported. The dioxomolybdenum(VI) complexes have been characterized by elemental analyses, molar conductance, UV-Vis, IR, mass, nmr spectra and thermal studies,. The probable coordination number of molybdenum is six. All complexes of dioxomolybdenum(VI) have octahedral geometry. O O + O O Ethanol 2 N N H2 2,3-Diamino-5-bromopyridine Furil N. .N Br 2H 2 O NH2 N O O NH2 Br Br N N H2 [L] O Ethanol 2H 2 O O O Mo ++ O O O Molybdenyl acetylacetonate O O O N. O O Mo N . Br N N. R [MoO Br  - diketone (acac) 2 N . Br N R 2 (mac)](acac) O O R 2H 2 O N N. O R N. O O Mo N H2 (acac) 2 N N H2 [MoO 2 (L)](acac) 2 Br 2 Type I Type II W h e r e, L = f u r il + 2 ,3 - d ia m in o - 5 - b ro m o p y ri d in e ; m ac = m a cr o c yc lic li g an d s ca r r ied o u t fr o m c o n d en s at io n o f L w it h β -d i k eto n es in p r es en ce o f d io x m o l y b d e n u m ( V I ) c ati o n ; R = ’ C H 3 , C 6 H 5 , C 4 H 3 S , C 6 H 5 ; R = C H 3 , C H 3 , C F 3 , C 6 H 5 ; r e sp e c tiv e β - d ik e to n e = ( i) ac ety la cet o n e, (ii ) b en z o y la cet o n e , (ii i) th en o yl tr if l u o r o a ce to n e, (iv ) d i b en z o ylm e th an e. [1] A. S. Ahamed, A. A. Saadia and A. Orabi, Spectrochim. Acta, 2006, 65A, 841-845. [2] D. P. Rao, H. S. Yadav, A. K. Yadava, S. Singh and U. S. Yadav, J. Serb. Chem. Soc. 2012, 77, 1205-1210. [3] G A Melson, Coordination Chemistry of Macrocyclic Compounds, New York, 1979. [4] D.P. Rao, H.S. Yadav, A.K. Yadava, S. Singh and U.S. Yadav, J. Coord. Chem., 2011, 64, 293-299. Acknowledgements - Gratitude is expressed to the UGC, New Delhi, India [project F. No. 39-740/2010 (SR)] financial support. The authors would like to thank the Secretary, Board of Management, D.A-V. P.G. College, Kanpur, U.P., India for providing laboratory facilities for research work. Analytical facilities provided by SAIF, IIT, Bombay, India and STIC, Kochi, India are gratefully acknowledged. e-mail: devendraprataprao@yahoo.com O26 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FACILE DESIGN OF COORDINATION COMPLEXES AND ORGANOMETALLICS USING ELEMENTOORGANIC LIGAND KIT Konstantin A. Rufanova and Ilya Yu. Titovb a M.V. Lomonosov University of Moscow, Chemistry Faculty, Moscow, RUSSIA b N.D. Zelinsky Institute of Organic Chemistry, Leninsky pr-t, 47 Moscow, RUSSIA Generalization of synthetic approaches towards coordination and organometallic complexes is a fundamental challenge. Importance of this task can scarcely be exaggerated. Systematic ligand design based on organoelement compounds of a genaral type R2E(X)Y, where E=P, S and X, Y = CHR, Cp(Ind or Flu), NR and O (S or Se) comprises a ligand kit thatr allows facile variation of ligand properties. _ Thus, for example, linked ~ H+ cyclopentadienylsilylamido A MLn Si Si Si H systems become one of the best N N NH established and developed class of specially designed ligand precursors. _ _ Bridged cyclopentadienylamido ~ H+ B complexes therefrom, better MLn P+ P+ P+ known as "constrained geometry N NH N catalysts", are analogous to ansametallocenes. Depending on the nature of the ligand framework _ _ ~ H+ these complexes give high C MLn molecular weight polyethylene S++ S++ S++ N with long chain-branching and NH N effeciently co-polymerize higher -olefins. Isoelectronic analogues of the A systems are linked cyclopentadienyl-phosphazenes (B) and cyclopentadienyl-thiazenes (C). Synthesis of a series of organometallics complexes, their catalytic applications and synthetic possibilities of elementoorganic ligand kit for design of new complexes will be discussed. E-mail: kruf@mail.ru O27 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia RECENT ADVANCES IN BORON CLUSTER NUCLEOSIDE CONJUGATES CHEMISTRY A. Semioshkina, V. Bregadzea, A. Ilinovaa, J. Laskova, I. Lobanovaa, M. Białek-Pietrasb and Z. J. Lesnikowskib a A.N.Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilov Str. 28, 119334, Moscow, RUSSIA. b Institute of Medical Biology, Polish Academy of Sciences, 106 Lodowa St., 93-232, Lodz, POLAND Development of methods for the synthesis of nucleosides bearing boron cages focuses growing attention in recent time. Potential application of these new type of bio-inorganic conjugates in medicine and biology range from their use as potential boron donors for BNCT of tumors and antiviral drugs1,2. In this contribution we would like to present our results on the synthesis of a series of cobaltbis-dicarbollide and closo-dodecaborate clusters conjugates with nucleosides. Synthesis of the desired compounds by action of the nucleophile-modified nucleosides with a range of cyclic oxonium adducts of cobalt-bis-dicarbollide and closo-dodecaborate clusters and biological investigations of some of them will be discussed. H B HB BH O B spacer O O BH BH 2BH BH HB BH NH BH HO B H N O O OH [1] Y. Byun, S. Narayanasamy, J. Johnsamuel, A.K. Bandyopadhyaya, ; R. Tiwari, A.S. AlMadhoun, R.F. Barth, S. Eriksson, W. Tjarks, Anti-Cancer Agents Med. Chem., 2006, 6, 127. [2] A.R. Martin, J.-J. Vasseur, M. Smietana, Chem. Soc. Rev. 2013, doi: 10.1039/C3CS60038F. Acknowledgements –We thank RFBR (11-03-0746, 12-03-31146) and POIG.01.01.02-10-107/09. e-mail: semi@ineos.ac.ru O28 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia THE REDOX TRANSFORMATIONS OF THE DIGALLIUM COMPLEX WITH REDOX-ACTIVE ACENAPHTHENE-1,2-DIIMINE LIGAND A.A. Skatova, I.L. Fedushkin, N.L. Bazyakina and V.A. Dodonov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Main group metal complexes of bis(1,2-arylimino)acenaphtene ligands are highly reactive towards different organic substrates and might be useful reagents in organic synthesis. Recently we have established [1] the facile addition of various alkynes to binuclear gallium complex supported with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN), (dpp-BIAN)Ga–Ga(dpp-BIAN) (1) and unusual thermally induced elimination of the alkyne. Compound 1 contains two redox-active centres – atom Ga(+2) and diimine ligand and therefore exhibits diverse reactivity: the reactions of the digallane may occur with metal-metal bond cleavage or with electron transfer from the ligand to the substrate. Thus reaction of a digallane with one equivalent of iodine or acenaphthene-1,2-quinone leads to the compounds [(dpp-BIAN)GaI]2 (2) and (dpp-BIAN)Ga(AcQ)Ga(dpp-BIAN) (3), containing gallium– gallium bond, whereas 1 reacts with 3,6-di-tert-butyl-o-benzoquinone (1:2) to give the monogallium catecholate complex (dpp-BIAN)GaCat (4), correspondingly. The oxidation of 1 with 2-phenyl-3-buten-2-one resulted in the bisenolate complex 5 containing new carbon– carbon bond. The compound 5 can be converted under heating to the initial digallane or to the monogallium complex. Ar N I Ar N Ga N Ar I O Ar Ga N N Ar O N N Ar 2 Ar Ga N Ga Ar 3 + iodine Ar N Ar N Ga + 3,6-di-tert-butylbenzoquinone N Ar + acenaphthene-1,2-quinone Ga 1 N Ar + 4-phenyl-3-buten-2-one Ph Ar N Bu-t N Ga Ar Ga N Ga N Ar Ar Bu-t 4 O N O N Ar O Ar O Ph acenaphthene parts are omitted for clarity 5 [1] I.L. Fedushkin, A.S. Nikipelov, A.G. Morozov, A.A. Skatova, A.V. Chekasov and G.A. Abakumov, Chem. Eur. J., 2012, 18, 255-266 Acknowledgements -This work has been supported by the Russian Foundation for Basic Research. e-mail: skatova@iomc.ras.ru, igorfed@iomc.ras.ru, nb@iomc.ras.ru, rohoros@gmail.com O29 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FERROCENES-BASED ANTICANCER DRUGS. FACTS AND HYPOTHESES L.V. Snegur a, A.A. Simenela, V.N. Babina, N.S. Sergeevab a A.N. Nesmeyanov Institute of OrganoElement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RUSSIA b P.A. Herzen Moscow Oncological Research Institute, 3, 2rd Botkinskiy pass., Moscow 125284, RUSSIA We investigated a large range of ferrocene compounds as anticancer drug candidates (Scheme). Antitumor effects of ferrocene derivatives of nucleobases, pyrimidines, and azoles including fluoroazoles against some murine tumor systems such as carcinoma 755, melanoma B16 and Lewis lung carcinoma were evaluated in vivo. Treatment of human ovary cancer cells with 1N-(ferrocenylethyl)adenine resulted in inhibition of DNA synthesis. Authors postulate that the mechanism of antitumor ferrocene compounds consists in the initiation of the tumor cell apoptosis by protection telomere from the action of telomerase and/or by decreasing telomerase activity. These conclusions are supported by unique physical, chemical and biological properties of ferrocene compounds. Synthetic approaches to ferrocene-modified biomolecules have been developed based on synthetically available hydroxyl(alkyl)ferrocenes (Scheme). 1. 2. 3. L.V. Snegur, V.N. Babin, A.A. Simenel, Yu.S. Nekrasov, L.A. Ostrovskaya, N.S. Sergeeva, Antitumor activities of ferrocene compounds (review), Russ. Chem. Bull., Int. Ed. 2010, 59, No 12, 2167-2178. L.V. Snegur, Yu.S. Nekrasov, N.S. Sergeeva, Zh.V. Zhilina, V.V Gumenyuk, ZA. Starikova, A.A. Simenel, N.B. Morozova, I.K. Sviridova, V.N. Babin, Ferrocenylalkyl azoles: bioactivity, synthesis, structure, Appl. Organomet. Chem., 2008, 22, 139-147. L.V. Snegur, S.I. Zykova, A.A. Simenel, et al., Redox-active ferrocene-modified pyrimidines and adenine as anticancer agents: X-ray structure, enantiomeric resolution, inhibition of DNA synthesis in tumor cells, Russ. Chem. Bull., Int. Ed. 2013, in press. Acknowledgements. This work was supported by the Russian Academy of Sciences (Presidium Program “Fundamental Sciences  for Medicine”), by the Department of Chemistry and Materials Science (Program “Medicinal Chemistry”) and by the Russian Foundation for Basic Research (RFBR No 09-03-00535). e-mail: snegur@ineos.ac.ru O30 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia THE OCTAHEDRAL IODIDE CLUSTERS OF Mo(II). SYNTHESIS AND LUMINESCENCE M.N. Sokolov, M.A. Mihailov, K.A. Brylev Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, pr-kt Akad. Lavrentieva 3, Novosibirsk, RUSSIA. The octahedral halide bridged clusters of Mo(II) possess remarkable photophysical properties which can be used for development of new fluorescent materials. New results on [Mo6I14]2chemistry will be presented. The anion [Mo6I14]2- is hydrolyzed in a solution of borate buffer at pH = 9.7, forming crystalline hydrates [Mo6I8(OH)4(H2O)2]·14H2 , [Mo6I8(OH)4(H2O)2]·12H2O, [Mo6I8(OH)4(H2O)2]·6H2O. X-ray analysis showed that the water molecules and hydroxide ligands are coordinated to the cluster core {Mo6I8}4+; in the first two hydrates the water molecules form three-dimensional frameworks that resemble the structure of different modifications of ice, where cluster core are located in large cavities. Starting from [Mo6I14]2- several types of new luminescent cluster complexes were obtained: carboxylate complexes with a general formula of [Mo6I8(OOCR)6]2- (R = C5H3O (α-furyl) (see figure 1), C10H7 (α-naphthyl), C4SH3, C6F5), nitrophenolate complexes [Mo6I8(OR)6]2(R = -C6H4NO2, -C6H3(NO2)2), thiolate complex [Mo6I8(SR)6]2- (R = C6F4H) and acetylenide complex [Mo6I8(CCR)6]2- (R = CO2CH3). The complexes were obtained by metathesis reactions between [Mo6I14]2- and corresponding silver salts, and characterized by X-ray analysis, mass-spectrometry and other methods. The acetylenide complex (Ph4P)2[Mo6I8(C2CO2CH3)6] containing six ligands of deprotonated methyl propiolate, is the first example of an homoleptic organometallic complex for octahedral clusters {M6Q8}. Luminescence properties of all new complexes were measured. The quantum yields and phosphorescence lifetimes depend on the external ligands in the following order: carboxylate > phenolate > thiophenolate > acetylenide. Among the carboxylates, introduction of fluorinated or aromatic groups improve the photophysical performance. In particular, perflurobutyrate (Bu4N)2[Mo6I8(C3F7COO)6] displays extraordinarily bright long-lived red phosphorescence, with the highest emission quantum yields among hexanuclear metal cluster complexes of Mo, both in acetonitrile solution (Φem = 0.59, em = 668 nm) and solid phases (Φem = 0.36, em = 659 nm). To conclude, unusually bright long-lived red luminescence can be expected for iodide cluster complexes of molybdenum with a fluorinated organic ligands, and the presence of conjugated systems in the structure of the ligand can greatly increase the luminescence intensity. + MeO(O)CCC– [{Mo6I8}I6] 2– [{Mo 6I8}(CCC(O)OMe)6] 2– e-mail: caesar@niic.nsc.ru O31 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia FERROCENYLTELLURIM HALIDE AND METAL-CARBONYL DERIVATIVES. Y. Torubaeva, P. Mathurc, M. Tauqeerb, A. Pasynskiia, M. Shaikhc a N.S. Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia b IIT-Bombay, India, c IIT-Indore, India.. Despite the relative amount of halogenating agent halogenation of diferrocenyl ditelluride (Fc2Te2) affords only mixed-valent ferrocenyl-tellurenyls [FcTe-TeX2Fc] (X=Cl (1), X=Br (2), X=I (3)). Unlike FcTe-TeCl2Fc (1) and FcTe-TeBr2Fc (2) revealing two signals in 125Te NMR spectrum, the single Fc Fc X 125 Te NMR resonance peak SO2Cl2, Br2, I Te Te 2 Te Te of iodo-(3) suggests the X Fc monomeric [FcTeI] Fc Fc = ferrocenyl structure in the solution at X = Cl, Br, I room temperature. In all three structures 1 - 3, nonhalogenated atom of TeII bents towards the Fe atom of ferrocenyl so that the deviation of Te(2) atom from the plane of the related Cp ring increases from 15.5° to 20.3° as we move . from the iodo- 3 to the chloro- 1 (the Fe(2)---Te(2) distance decreases from 3.3714(6) Å in the iodo- 3 to 3.293(3) Å in the chloro- 1 ). This lays within the range of 14.6° ~ 20.7° observed in -ferrocenyl carbocations [C5H5FeC5H4C(C6H5)2]+[BF4][1], + - 2 [C5H5FeC5H4(cyclo-C3(C6H5)2)] [BF4] [ ] for which the interaction of filled nonbonding 3d t2g orbitals of Fe with the LUMO of carbocation moiety was assumed. Similar, but less pronounced bent of non-coordinated Te atom towards the Fe atom of ferrocene was observed in M(CO)5(Fc2Te2) – products of diferrocenyl ditelluride (Fc2Te2) interaction with VIb group metal carbonyls, Fe let us suggest the analogous interaction of X   filled nonbonding 3d t2g Te Te Te Te Fe Fe d Fe d orbitals of Fe with the X M(CO) tellurium localized LUMO. Shortening of 20.3X = Cl 9X = Cr 15.4X = Br M-Te distance and 8X = Mo 15.4X = I 7X = W corresponding elongation of Te-Te and Te-C distances in these complexes occurs due to and depends on the back donation of metal dorbitals to Te-Te and Te-C localized LUMO of Fc2Te2 ligand. Acknowledgements We gratefully acknowledge the financial support from the Department of Science and Technology (Govt. of India), University Grants Commision (UGC, India). Russian Foundation for Basic Research (project 12-03-33101a, 12-03-00860 and 13-03-92691), Department of Chemistry and Material Sciences of RAS (grant OKh 1.3), Presidium of RAS (grant 8P23) and RF President Fellowship (MD 7122.2012.3) References: 1. U. Behrens, L Organomet. Chem. 1979, 182, 89-98. 2 . R. L. Sime , R. J. Sime. J. Am. Chem. Soc., 96 (1974), 3, 892–896 5 e-mail: torubaev@gmail.com O32 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia OBTAINING OF ANTIREFLECTIVE COATINGS ON THE BASIS OF NANOPOROUS SILICON DIOXIDE AT LOW TEMPERATURE ANNEALING GEL B. Troitskii, V. Denisova, A. Lokteva, M. Novikova, M. Lopatin, T. Lopatina, Yu. Chechet G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The sol-gel process becomes one of the most important ways to obtain various inorganic and composite organic-inorganic film coatings on glass, metals, and polymers. It has been found recently [1–8] that addition of nonsurfactant organic compounds (organic acids, their derivatives, synthetic carbochain polymers, statistical copolymers, and oligomers based on ethylene or propylene oxide) to a silicon dioxide sol makes it possible to obtain film coatings with strong antireflection effect on glass and quartz. However, the film coating deposited from a sol onto silicate glass was annealed at an elevated temperature of 500°C for several hours in order to obtain nanoporous silicon dioxide. The goal of our study was to examine the optical properties of coatings and glass with coatings produced from silicon dioxide sols with addition of poly(propylene glycols) (PPGs) with various molecular masses and a gel annealing temperature of 200°C. The results of present work: 1) Annealing of silicate glass with a film coating deposited from silicon dioxide sols with addition of PPG-425, PPG-725, PPG-1000, PPG-2700, PPG-4000 at a low temperature 200°C yields antireflection coatings composed of nanoporous silicon dioxide with low refractive index 1.26–1.30. 2) The optical transmission of a coated glass depends on the content of an additive in the sol and has the maximum values of 98.2% at 6.0% PPG-425, 97.7% at 6.0% PPG-725, 98.7% at 6.0% PPG1000, 97.9% at 4.0% PPG-2700, and 97.5% at 4.0% PPG-4000. 3) With increasing content of a PPG in the sol, the peaks in the optical transmission curves for a coated glass shift to longer wavelengths, and this effect becomes more pronounced as the molecular mass of a PPG increases. [1] B.B.Troitskii, A.A. Babin, M.A. Lopatin, et al., Izv. Akad. Nauk, Ser. Khim., 2008, 2408–2411. [2] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al., Zh. Prikl. Khim., 2008, 81,1365–1369. [3] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al, RF Patents: 2368575, 2009; 2371399, 2009; 2368576, 2009; 2466948, 2012. [4] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al, Zh. Prikl. Khim., 2009, 82, 935–938. [5] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al, Fiz. Khim. Stekla, 2010, 36, 767–777. [6] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al, Izv. Akad. Nauk, Ser. Khim., 2010, 681–684. [7] B.B.Troitskii, V.N. Denisova, M.A. Novikova, et al, Zh. Prikl. Khim., 2012, 85, 402–406. [8] B.B.Troitskii, A.A. Lokteva, V.N. Denisova, et al, Zh. Prikl. Khim., 2013, 86, 525–529. Acknowledgements – RFBR (grant 13-03-97026) e-mail: troitski@iomc.ras.ru O33 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia POLYARYLENCARBORANES: FROM C-FUNCTIONALIZED BIPHENYL-O- AND M-CARBORANES TO LINEAR AND THREE-DIMENSIONAL POLYMERS WITH RECORD HEAT AND THERMO-OXIDATIVE STABILITY P.M. Valetskya, Y Kabachya, S.V. Vinogradovaa, L.I. Golubenkovab, A.P. Petrovac a A.N. Nesmeyanov Institute of organoelement Compounds Russian Academy of Science, 119991, Vavilova str.,28, Moscow, RUSSIA; b G.S. Petrov Scientific Research Institute of Polymer Plastic Materials, 111024, Perovsky str., 35, Moscow, RUSSIA c All-Russian Scientific Research Institute of Aviation Materials 105005, Radio str., 17, Moscow, RUSSIA In Memory of prof., academician V.V. Korshak and prof. V.I. Stanko. The report describes the history of development of carborane (12) containing monomers by Cfunctionalization of bis (4-phenyl) ortho-, meta- and in some cases para-carboranes, starting from the corresponding tolanes and decaborane, and also synthesis and properties of linear and threedimensional polymers - polyarylencarboranes (PCAR). The properties of PCAR are compared to their aromatic analogs. The essential difference of PCAR is unusual behavior at elevated temperatures in oxidizing medium (air), inert atmosphere or in vacuo: crosslinking at relatively low temperatures, low release of volatile compounds during heating until 1000°C. It was found that reasons of such unusual thermal and thermo-oxidative behavior of PCAR consist predominantly in reacting generated boron-centered free radicals with aromatic surrounding of polymer matrix. Formation of boron-centered stable radicals has been first described in example of carborane-12. This in turn gave rise to the creation of carborancontaining monomers and polymers based on aromatic B-C and B-C unsaturated compounds. For example, first synthesis of carboranyl-B(3,6)-p-phenyltrichlorosilanes was done - an important intermediate for producing crosslinked polycarboranylphenylsilanes. With the participation of GNIICHTEOS the appropriate setup was created at the plant "AVIABOR", Dzerzhinsk. The process was terminated due to the privatization of the company and change its technology policy. The data on the materials (adhesives, hermetics, carbon plastics) with record thermal and thermo-oxidative properties are given. The development of materials based on PCAR was carried out jointly with NIIPLASTMASS, VIAM, GNIIChTEOS and other companies. 1. .И., . ., . ., - // 39(3), 573 (1969); . ., я . ., . ., .И., . . 1,2. ., я , 15(10), 2200 (1973); . ., .И., . ., Ф . 19; . . , . . , . . , . . , .И. . 4-2,4,6- -2,5-12413; . . , . . , . . , . . 1180 (1985); . .К , .И. , . . , . . я я -12 // . ., . ., . ., // . , 64, 390-413 (1995). . ., .И. ( - )- - 2. 3. 4. 5. 6. 7. e-mail: vpyotr@gmail.com O34 .И., . ., . ., // . ., . // .И., , . . , . . , .И. -, -, -12. . ., 1984, . // И . .И , . . . . . , 1974, № 2, я // . , . .К . , 280, 1390 (1985); , 280, International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia MODIFICATION OF IRON(II) CLATHROCHELATES BY RADICAL REACTIONS M. Vershinin A. V. Nikolaev Institute of Inorganic Chemistry of Russian Academy of Sciences, 630090, Lavrent'ev Av, 3, Novosibirsk, RUSSIA. Tris-dioximate transition metal clathrochelates are promising molecular scaffolds for design of the polytopic molecules and polyfunctional materials [1]. Earlier [2], we have reported the functionalization of the dichlorine-containing boron-capped iron(II) macrobicyclic clathrochelate with different substrates using free-radical substitution. This reaction proceeds as a radical addition-elimination at the azomethine C=N bond of the dioxime fragment (Scheme) and can be extended to cyclic ethers, alcohols, esters and alkanes. In all cases studied we observed chlorine atom elimination and the formation of new C–C bonds at the azomethine fragment. In continuation of this research, we try to use dimethylsubstituted iron(II) clathrochelate in such reactions. In this case clathrochelate reacts similarly to oxime ethers and hydrazones via addition of alkyl fragments to double C=N bond. F B F B Ph Ph O R O O Ph N N R N X Fe X NPh N N O O O B F R . Ph O O O N Ph N N Fe X R Ph N Ph N X -X O X =CH3 F B N O O B F . Ph . X =Cl Ph O O O Ph N N N Fe NPh N N O O O B F The clathrochelate complexes obtained were characterized by single-crystal X-ray crystallography and 1H, 13C-NMR. [1] Y.Z. Voloshin, N.A. Kostromina, R. Krämer, Clathrochelates: synthesis, structure and properties, Elsevier, Amsterdam, 2002. [2] M.A. Vershinin, A.B. Burdukov, I. V. Eltsov, V. A. Reznikov, E. G. Boguslavsky, Y.Z. Voloshin, Polyhedron, 2011, 30 (7), 1233-1237. Acknowledgements - This study was supported by RFBR grant 10-03-00403. e-mail: m.vershinin@ngs.ru O35 R X International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” September 1-7, 2013, N. Novgorod, Russia COBALT-INDUCED B-H AND C-H ACTIVATION LEADING TO FACILE B-C COUPLING OF CARBORANEDITHIOLATE AND CYCLOPENTADIENYL R. Zhang, L. Zhu and H. Yana* a State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, P. R. CHINA We report the one-pot reactions of the 16e half-sandwich complex CpCoS2C2B10H10 (1), methyl propiolate and 3e-donor ligands which have led to selective B-functionalization at carborane with cyclopentadienyl as a functional group at ambient temperature in good yields. Metal-promoted activations of both B–H bond at carborane and C–H bond at Cp unit have taken place sequentially in the cooperation of organic ligands. The reaction requires a 3edonor ligand and an activated alkyne, therefore suitable for a broad range of substrates. This investigation provides a simple and efficient synthetic route to B-functionalized carborane derivatives. [1] R. Zhang, L. Zhu, G. F. Liu, H. M. Dai, Z. Z. Lu, J. B. Zhao and H. Yan*, J. Am. Chem. Soc., 2012, 134, 10341. [2] M. Herberhold*, H. Yan, W. Milius and B. Wrackmeyer*, Angew. Chem., Int. Ed., 1999, 38, 3689. Acknowledgements - National Natural Science Foundation of China (20925104). e-mail: hyan1965@nju.edu.cn O36 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia International Youth SchoolConference on Organometallic and Coordination Chemistry International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NEW HYBRID Nb AND Ta POLYOXOMETALATES FUNCTIONALIZED WITH ORGANOMETALLIC COMPLEXES P.A. Abramov Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, pr-kt Akad. Lavrentieva 3, Novosibirsk, RUSSIA. Grafted noble metals on polyoxometalates (POM) can find applications in different catalytic applications [1, 2]. The hottest research area of such complexes is the photocatalytic water splitting [3]. In this case soluble POMs of Nb can be used as analogs of insoluble TiO2 and POMs of Ta are soluble analogs of NaTaO3. Synthesis of various complexes of {(pcym)Ru}2+ (p-cym = cymene) with [Nb6O19]8- with Ru/POM stoichiometries 1:1, 2:1, 3:1 and 4:1 was reported in 2007 [4]. We have found that reaction of [(C6H6)RuCl2]2 and Na8[Ta6O19] gives, depending on the reagent ratio, two new hybrid organometallic-POM complexes – Na10[{(C6H6)RuTa6O18}2( -O)]·39.4H2O (1:1 ratio, Fig. 1) and Na4(trans[{(C6H6)Ru}2Ta6O19]·20H2O (2:1 ratio, Fig. 2). In both cases the half-sandwich fragments {(C6H6)Ru}2+ are coordinated as additional vertices to the {Ta3( 2-O)3} triangles. The complexes have been characterized with x-ray structural analysis, NMR, IR, EA and CE. In water [{(C6H6)RuTa6O18}2( -O)]10- yields monomeric [(C6H6)RuTa6O19]6- which forms different protonated species. The trans-[{(C6H6)Ru}2Ta6O19]2- in water solution isomerizes into cis-form, the isomers ratio being trans:cys 60:40. Fig. 1. Fig. 2. Reaction between [M6O19]8- (M = Nb, Ta) and [Cp*RhCl2]2 in water gives a mixture of hybrid complexes with {Cp*Rh}: [M6O19]8- ratios of 1:1, 2:1 and 3:1. Crystallization from reaction mixture gives only K+ and Cs+ salts of trans-[{Cp*Rh}2M6O19]4-. In the case of [Cp*IrCl2]2 the formation of [{Cp*Ir}2M6O19]4- also takes place, but according to ESI-MS data, species with Ir(IV) were also detected. [1] D.Laurencin, R. Villanneau and A. Proust Tetrahedron: Asymmetry 2007, 18, 367. [2] Li-H. Bi, G. Al-Kadamany, E.V. Chubarova Inorg. Chem. 2009, 48, 10068 [3] H. Lu, Y.V. Giletti and C.L. Hill Chem. Soc. Rev. 2012, 41, 7572. [4] D. Laurencin, R. Thouvenot, K. Boubekeur Dalton Trans. 2007, 1334 Acknowledgements – The study was supported by The Ministry of education and science of Russia, project 14.B37.21.0820 and President of Russian Federation fellowship. The work was also supported by RFBR grant 13-03-00012. e-mail: abramov@niic.nsc.ru Y1 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia TRIS(HYDROXYMETHYL)PHOSPHINE TRANSITION METAL COMPLEXES: FROM MONO- TO POLYNUCLEAR COMPOUNDS A.V. Anyushina,b, D.A. Mainichevb a Nikolaev Institute of Inorganic Chemistry of Russian Academy of Sciences, 630090, Acad. Lavrentiev Ave., 3, Novosibirsk, RUSSIA. b Novosibirsk State University, 630090, Pirogova Str., 2, Novosibirsk, RUSSIA. Cluster and polynuclear complexes have a number of properties, such as fluorescence, redox activity etc, which may yield in various application areas, for example, in development of new analytical and diagnostic agents, catalysis etc. However, a major obstacle for the applied use of these compounds is their low solubility in aqueous media/hydrophobicity caused by coordination of hydrophobic organic ligands which are common in this chemistry. This problem can be solved by introduction of special ligands such as tris(hydroxymethyl)phosphine (THP) which belongs to phosphine ligands which are known to stabilize such complexes and, on other hand, is hydrophilic and may be chemically modified. Only a few known examples of metal-sulfide complexes with THP are known, while polynuclear compounds with THP were not known at all. The purpose of this work is to develop a convenient method of obtaining the cluster and polynuclear complexes with THP and further modification of coordinated THP ligands to tune the properties. Synthesis technique was developed for 8-10 groups sulphide-metal clusters with THP. We, therefore, have obtained 14 new compounds: 11 water-soluble sulfide cluster transition metal complexes with THP and 3 coordination polymers of Cd containing THP oxidation products. It was shown that THP may be involved in condensation to form a bidentate ligand (HOCH2)2PCH2OP(CH2OH)2 during the synthesis of polynuclear complexes. We have also shown that coordinated THP may be acylated by acetic anhydride to give P(CH2OC(O)CH3)3 ligands without destruction of metal-sulfide cluster core. Stoichiometry of THP and Cd2+ interaction was defined and the parameters of the transition state complex were determined. Three coordination polymers based on Cd2+ and THP oxidation products were synthesized. The donor ability of THP was evaluated in comparison with PMe3 and PPh3. H2S CH3OH [M(P(CH2OH)3)2]Cl2 [M3(3-S)2(P(CH2OH)3)6]2+ . [Pt3S2(P(CH2OH)3)6]2+ (1), (2) . RhCl3 xH2O + P(CH2OH)3 [Ni3(3-S)2(P(CH2OH)3)6]2+ (3) [Ni3(3-S)2((HOCH2)POCH2P(CH2OH)2)3][Mo6Cl14] 0.8H2O (4) H2S CH3OH RuCl3 xH2O + P(CH2OH)3 [Rh3(3-S)2(2-S)(2-Cl)2(P(CH2OH)3)6]Cl (5) . CH3OH [Ru2(2-Cl)3(P(CH2OH)3)6]Cl (6) [Ru(PPh3)3Cl2] + P(CH2OH)3 1). (RCO)2O H2S [M6(3-S)8(P(CH2OH)3)6]n+ MCl2 xH2O + P(CH2OH)3 2). C2H5OH CH3OH M = Fe (7), n = 2 M = Co (8), n = 0 {Cd(P(CH2OH)3)3}solv (11) CdCl2 xH2O + P(CH2OH)3 CH3OH . . [CdCl2(OP(CH2OH)3)] (13) [M6(3-S)8(P(CH2OC(O)R)3)6] M = Co (9), n = 0, R = CH3 M = Co (10), n = 0, R = C2H5 [Cd3Cl6(OP(CH2OH)3)2] (12) [Na2CdCl2(O2P(CH2OH)2)2(H2O)3] (14) Acknowledgements – RFBR grant No. 13-03-01261 for financial support e-mail: anjushin@niic.nsc.ru, dim@niic.nsc.ru Y2 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia PALLADIUM NANOPARTICLES STABILASED BY STERICALLY HINDERED PHOSPHONIUM SALTS AS AN EFFECTIVE SUZUKI REACTION CATALYST D. Arkhipovaa, V. Ermolaev, V. Miluykov, O.Sinyashin a A.E. Arbuzov Institute of Organic and Physical Chemistry KSC RAS 420088, Arbuzov str. 8, Kazan, RUSSIA. Palladium nanoparticles are effectively used as the catalyst in transition metal catalysed reactions such as Suzuki cross-coupling [1,2]. The problem of nanoparticles aggregation could be solved by using sterically hindered phosphonium salts (Scheme 1) as stabilizers. Scheme 1. Synthesis of the phosphonium salts. Scheme 2. Palladium self-recovery. Palladium nanoparticles were obtained in situ by stirring of palladium acetate in ethanol in the phosphonium salt presence (Scheme 2). The palladium nanoparticles formation has been proved by electron microscopy (Fig. 1). Scheme 3. The Suzuki reaction. A number of synthesized phosphonium salts was tested as the stabilizers of palladium nanoparticles in Suzuki cross-coupling of 1,3,5-tribromobenzene (1) and phenylboronic acid (Scheme 3). The results of catalysis are shown in Figure 2. t + - Conversion degree (1) to (2), % Bu P C10H21BF4 t + Bu P C10H21(CF3SO2)2N n + Bu P C10H21BF4 n + Bu P C10H21(CF3SO2)2N Phosphonium salt / palladium ratio Figure 1. Palladium nanoparticles stabilized by ButP+C10H21BF4-. Figure 2. Influence of structure and concentration of the phosphonium salt on conversion degree (1) to (2). [1] F. Alonso, I.P. Beletskaya, M. Yus, Tetrahedron, 2008, 64, 3047. [2] J D. Scholten, B. C. Leal, J. Dupont, ACS Catal., 2012, 2, 184−200. Acknowledgements – authors are grateful for the financial support to the Ministry of Education and Science of the Russian Federation (8451, MK 4440.2013.3). e-mail: ermolaev@iopc.ru. Y3 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPLEXES OF YB (II) IN CATALYSIS OF INTERMOLECULAR HYDROAMINATION AND HYDROPHOSPHINATION OF OLEFINS I. Basalova, D. Lyubova , G. Fukina, A. Cherkasova, S.-C Roșcab, Y. Sarazinb, J.-F. Carpentierb and A. Trifonova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b University of Renneas, Rennes, FRANCE Catalytic reactions of hydroelementation of C–C unsaturations attract a great deal of attention due to the 100% atom economy involved in these reactions. Application of this approach could lead to the development of new environmentally friendly green technologies. In addition, the products formed in these processes are used in pharmaceuticals, organic synthesis and materials science. The reaction rates of the hydroelementation reactions are known to increase with increasing ionic radius of the metal center. Therefore, the use of compounds of divalent lanthanides with large ionic radii, is a promising direction in the development of catalytic reactions of intermolecular hydrophosphination and hydroamination of olefins. In order to investigate the catalytic activity in hydroamination and hydrophosphination reactions a series of amido and hydrido Yb (II) complexes stabilized by various ligand systems were synthesized: [{tBuC(NC6H3-2,6-iPr2)2}YbN(SiMe3)2(THF)] (1), [{tBuC(NC6H3-2,6-iPr2)2}Yb(µ-H)}2] (2), [{tBuC(NC6H3-OMe)(NC6H3-2,6iPr2)}YbN(SiMe3)2(THF)] (3), [{3,5,10,12-tBu4C13H4N}YbN(SiMe3)2(THF)] (4), [{2-(N-2,6iPr2C6H3)-6-(2,6-Me2C6H3)-C5H3N}YbN(SiMe3)2(THF)] (5), [{MeC[(N-2,6Me2C6H3)2(NC6H3)][(NC6H3-2,6-iPr2)]}YbN(SiMe3)2(THF)] (6), [{O-2,4-tBu2-6-(12-crown5)C6H3}YbN(SiMe3)2 ](7). It was found that the synthesized compounds exhibit a catalytic activity in intermolecular styrene hydroamination and hydrophosphination reactions. All reactions were found to be regioselective, forming exclusively the Anti-Markovnikov addition product. These catalysts allow carrying out intermolecular hydroamination and hydrophosphination reactions at 60oC with quantitative conversions without using a solvent. Figure 1. 1) Hydrophosphination of styrene and HPPh2; 2) hydrophosphination of styrene and H2PPh; 3) hydroamination of styrene and pyrrolidine catalyzed by Yb(II) complexes. Acknowledgements - This work was supported by RFBR (12-03-93109И _a) and grant of President of Russian Federation for state support of young Russian scientists (MK-4908.2012.3) e-mail: basalov.vania@yandex.ru, trif@iomc.ras.ru Y4 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESES, STRUCTURES AND LUMINESCENT PROPERTIES OF THE TRANSITION METAL COMPLEXES CONTAINING 2,1,3-BENZOTHIADIAZOLE DERIVATIVES D. Bashirova, T. Sukhikha, A. Zibarevb, S. Konchenkoa, V. Muravyovc, A. Mustafinad a Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, Acad. Lavrentiev ave, 3, Novosibirsk, RUSSIA b Institute of Organic Chemistry, SB RAS, 630090 Novosibirsk, Acad. Lavrentiev ave, 9, RUSSIA c Novosibirsk State University, 630090 Novosibirsk, Pirogova str, 2, RUSSIA d A.E. Arbuzov Institute of Organic and Physical Chemistry Kazan, 420088, Arbuzov str., 8, Kazan, RUSSIA 2,1,3-benzothiadiazole derivatives are promising building blocks for design of molecular magnets and conductors. Furthermore, due to their photophysical properties the benzothiadiazoles can be used as components of organic light emitting diodes (OLED). For OLED applications, these heterocycles are interesting not only as structural units of polymers but also as ligands in transition metal complexes [1]. Recently we described the syntheses of the iridium complexes containing 2,1,3-benzothiadiazole (btd) and its 4-hydroxy- (OH-btd) and 4-amino- (NH2-btd) derivatives [2]. Herein we report about their luminescent properties and about syntheses, structure and some physical properties of the ruthenium, zinc and yttrium complexes of OH-btd and NH2-btd. N N S S N S N OH btd N N NH2 OH-btd NH2-btd Reactions of NH2-btd with ZnCl2 and Y(N(SiMe3)2)3 and OH-btd with [{Ru(bpy)2}2(OMe)2] have been investigated. It has been shown that NH2-btd is a week acid and can react as neutral molecule or deprotonated (NH-btd–) anion. In the first case it coordinates a metal by NH2group, in the other one both by NH– and N atom of heterocycle. Structures of the complexes [ZnCl2(NH2-btd)2], [Y2(NH-btd)6(THF)] and [Ru(bpy)2(O-btd)](PF6) have been confirmed by single crystal X-Ray diffraction and other routine methods. Furthermore luminescent properties of the iridium and ruthenium complexes have been studied. It has been shown that emission wavelength depend only of the heterocycle nature. [1] B. A. D. Neto, A. A. M. Lapis, E. N. da Silva Júnior, et al, Eur. J. Org. Chem. 2013, 228–255 [2] D.A. Bashirov, T.S. Sukhikh, N.V. Kuratieva, et al. Polyhedron 2012, 42, 168-174 Acknowledgements – The authors are grateful to the Russian Foundation for basic research (grants No. 12-0331530, 12-03-31759, 13-01-01088), and Federal target program "Kadry" (Contract No. 8631) for financial support. e-mail: bashirov@ngs.ru, konch@niic.nsc.ru Y5 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia STRUCTURAL FEATURES OF THE HETEROMETALLIC COMPLEXES VIVO-MII (MII = MnII, CoII, CdII) BASED ON SUBSTITUTED MALONIC ACID ANIONS E. Bazhina, G. Aleksandrov, A. Sidorov, and I. Eremenko N. S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky prosp, 31, Mocsow, RUSSIA. In present work we have studied the possibility of formation of the new heterometallic complex compounds with combination of metals VIV-MnII, VIV-CoII, VIV-CdII and dimethylmalonic, (H2Me2mal), butylmalonic (H2Bumal) and cyclobutane-1,1-dicarboxylic (H2Cbdc) acid anions. Compounds 1-5 of general formula {[MII(VIVO)L2(H2O)5]·H2O}n, where 1: MII = MnII, L = Me2mal; 2: MII = CoII, L = Me2mal; 3: MII = MnII, L = Bumal; 4: MII = CdII, L = Bumal; 5: MII = CdII, L = Cbdc were obtained in crystalline form and characterized by X-ray diffraction analysis. Complexes 1-5 crystallize from water solutions, obtained by interaction of vanadyl sulfate VOSO4·3H2O solution, d-metal MII sulfate and barium salt of the corresponding dicarboxylic acid BaL in the ratio 1:1:2. Compounds are built on the base of dianionic metal fragments {VOL2(H2O)}2-, in which the vanadium(IV) atom chelates two substituted malonic acid dianions, one water molecule and the oxygen atom of the vanadyl group {V=O} forming distorted octahedral oxygen environment. In structures 1-5 bis-chelate fragments linked with MnII, CoII and CdII atoms through the acid dianion carboxylate oxygen atoms, which are not coordinated by vanadium(IV) atoms, forming polymeric chains. Heteroatoms complete octahedral coordination environment with four atoms of water molecules. a b Fig. 1. Fragments of polymeric chains of compounds 4 (a) and 5 (b). In binding vanadium(IV) and d-metal atoms in complexes 1-4 both malonate anions of bischelate fragment {VOL2(H2O)}2- take part, and each anion binds vanadium-containing fragment with one d-metal atom. Unlike them in compound 5 only one of the ligand anions takes part in binding {VOL2(H2O)}2- fragments with Cd atoms, linking together three metal atoms at once; the second anion of the bis-chelate dianionic fragment performs only chelate function (Fig. 1). Acknowledgements – This study was supported by the Russian Foundation for Basic Research (projects no. 1103-00735 and 12-03-31151), the Russian Academy of Sciences, the Council on Grants of the President of the Russian Federation (grant NSh-2357.2012.3). e-mail: evgenia-VO@mail.ru, sidorov@igic.ras.ru. Y6 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia STUDY OF THE FISCHER- TROPSCH SYNTHESIS IN THE PRESENCE OF A NANOSTRUCTURED IRON OXIDE-POLYMER CATALYST M.I. Biriukova, G.Yu. Yurkov, Buznik B.M. Baikov Institute of Metallurgy and Material Sciences Russian Academy of Sciences, 119991, Leninsky pr. 49, Moscow, Russia The Fischer-Tropsch process is a catalytic reaction between carbon monooxide and hydrogen yielding a mixture of liquid hydrocarbons. Catalyst used for the process normally contain iron or cobalt. The key application of the process is production of synthetic lubricants and oil. Iron oxide (Fe2O3, FeO, Fe3O4) nanoparticles catalyse reactions which involve allylic chloroolefins, such as isomerisation with the double bond and chlorine atom migration or alkylation of aromatic hydrocarbons. The catalysis efficiency and dominating reactions depend on the presence of oxygen, oxidation state of iron atoms and the immediate environment of the nanoparticles in the catalyst. Composites consisting of low density polyethylene (LDPE) impregnated with ironcontaining nanoparticles were prepared by thermal decomposition of iron nitrate in a solutionmelt of LDPE in oil at 240–260 ° in inert atmosphere; the prepared samples were consequently stored in air. The size of the nanoparticles did not exceed 2–4 nm. The catalyst was mixed with the P-2 paraffin before the Fischer-Tropsch synthesis; the catalyst completely dissolved in the paraffin and formed a stable suspension. The reaction was carried out under vigorous stirring (400 rpm) in an autoclave flow-through reactor. The catalyst was subject to preliminary activation in a carbon mooxide flow (14 nl/g(Fe)·h) at 300 ° and 20 atm for 20 hours. The catalyst was found to be inactive at low temperatures, but its activity rises during conditioning resulting in higher CO conversion ratios at higher temperatures. The CO conversion ratio at 300 ° is 80%, and the liquid products yield becomes as high as 138 g/m3. On the other hand, liquid product selectivity decreases from 84% at 240 ° to 54% at 300 ° . The selectivity decrease is mainly due to the water-gas side reaction. The catalyst exhibits high throughput (2228 g/kg(Fe)·h at 300 ° ). The liquid product formed on the catalyst consists of two layers: the aqueous layer with oxigenate compounds and hydrocarbon layer. Hydrocarbon products formed during the synthesis include both saturated and unsaturated hydrocarbons (the content of the latter does not exceed 39% wt.) An important parameter of the Fischer-Tropsch process is the chain growth probability α which can be used as an indicator of the polymerization activity; the tested catalyst has α = 0.58. The composition of the hydrocarbon product is: 77% wt. gasoline fraction, 22% wt. diesel fraction, < 1% wt. solid aliphatic hydrocarbons. E-mail: marino4cka.b@yandex.ru The work was financially supported by the RFBR grant no. 11-08-00015a and RAS Presidium Basic reasearch program P-8, O -7. Y7 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NEW BIFUNCTIONAL QUINONE WITH TETRATHIAFULVALENE BRIDGE. SYNTHESIS, STRUCTURE AND PROPERTIES. N.O. Chalkova, V.A. Kuropatovb and V.K. Cherkasovb a N.I.Lobachevsky Nizhny Novgorod State University, 603950, Gagarin ave, 23, Nizhny Novgorod, RUSSIA. b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinin str, 49, Nizhny Novgorod, RUSSIA. Organic redox-amphoteric compounds have great scientific interest because of their ability to oxidize and reduce reversibly relatively neutral state. Combination in one molecule acceptor and donor units leads to organic redox-amphoteric compounds. Nowadays acceptor-donoracceptor (A-D-A) triads are extensively studied systems. Here we present a new bifunctional quinone with p-extended tetrathiafulvalene moiety as example of A-D-A triad. Synthesis of novel compound was carried out through three steps. First of all, dichloro-p-xylylene was prepared. Then it was converted into sodium tetrathioterephtalate. Final stage is stoichiometrical interaction between two equivalents of 4-chloro-3,6-di.tert.butyl-obenzoquinone and one equiv sodium tetrathioterephtalate (scheme 1). Product was isolated as rectangle shaped black needle crystals and characterized with physicochemical analysis methods. Taking into account IR -, NMR-spectroscopy and X-ray data, we have supposed that charge transfer process is proceeded in bifunctional quinone molecule. t-Bu O S S THF + 2 Cl NaS O SNa -2 NaCl t-Bu t-Bu t-Bu O THF -2 NaCl O S S S S t-Bu O Picture 1. Structure of bifunctional quinone with tetratiafulvalene bridge. O t-Bu Scheme 1. Chemical reduction of bis-o-quinone as ligand has been studied (scheme 2). Bifunctional quinone contains four hydrogen atoms at the central phenylene ring. This fact substantially gains an amount of information which can be obtained from EPR spectroscopy data. EPR and UV spectroscopy simultaneous study reveals a sequential formation of two different paramagnetic species during chemical reduction of quinone with metal sodium. On the first stage dimeric radical anion particle with formal oxidation state -1/2 was generated (Robin-Dei III-rd class). Second compound is o-semiquinone metal complex. These two intermediate compounds have different signals in EPR spectra. O t-Bu t-Bu O S O S S S t-Bu S S O t-Bu +M 2 O .- t-Bu O t-Bu O S S t-Bu t-Bu t-Bu O S t-Bu M t-Bu O S t-Bu t-Bu O t-Bu t-Bu S +M O S + M S O t-Bu S +M O +M + O S S O O t-Bu O S S O O S S O + + M M t-Bu t-Bu t-Bu Scheme 2. Acknowledgements - This scientific research was performed with financial support of the Russian Foundation for Basic Research, grants 13-03-01000-A and the Program for support of Leading Scientific Schools NSh1113.2013.3. e-mail: n.chalkov@iomc.ras.ru Y8 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia FIRST EXAMPLE OF CAGE-LIKE METALLASILOXANES USED AS CATALYSTS IN HOMOGENEOUS OXIDATION OF C–H COMPOUNDS M. Dronovaa, G.B. Shul’pinb, L.S. Shul’pinaa, E. Shubinaa, M. Levitskya, A. Bilyachenkoa, A.D. Kirilina a Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str., 28, Moscow 119991, RUSSIA b Semenov Institute of Chemical Physics, Russian Academy of Science, Ulitsa Kosigina, dom 4, Moscow 119991, RUSSIA Oxidation of hydrocarbons, alcohols and other C–H compounds with peroxides is an important field of contemporary metal-complex catalysis. We revealed a significant potential of cage-like Cu(II)-silsesquioxanes for the homogeneous (acetonitrile solution) oxidation of several C-H substrates by aqueous hydrogen peroxide under mild conditions (temperature <70°C). Such observation is very attractive due to convenient synthesis of catalysts, their low cost and stability. It has been also revealed that the course of the reaction is highly influenced by cage geometry and nature of co-catalysts. This work was supported by the Russian Foundation for Basic Research (grants No. 11-03-00646 and 1203-00084) e-mail: dronovamarina@gmail.com Y9 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURE AND MAGNETIC PROPERTIES OF HIGH-SPIN MANGANESE CARBOXYLATES I. Evstifeev a, M. Kiskin a, A. Lytvynenko b, A. Bogomyakov c, N. Efimov a, S. Kolotilov b, I. Eremenko a, V. Pavlishchuk b a N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, GSP-1, RUSSIA b L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 03028, UKRAINE c International Tomography Centre, Siberian Branch, Russian Academy of Sciences, Institutskaya str. 3a, 630090 Novosibirsk, RUSSIA High-spin polynuclear complexes and coordination polymers of 3d metals, especially of manganese(II), attract attention due to their magnetic properties. Such compounds can reveal magnetic ordering, magnetic hysteresis, etc. In this work new results in the field of new manganese compounds synthesis, investigation of their structure and magnetic properties are presented. Destruction of the polymer [Mn(Piv)2(EtOH)]n (Piv = pivalate) by chelating and bridging N-donor ligands (pyrimidine (prm), pyrazine (prz), 2,2'-bipyridine (bpy) and 1,10phenanthroline (phen)) was studied. Reaction of [Mn(Piv)2(EtOH)]n with pyrimidine in inert atmosphere resulted in formation of hexanuclear complex MnII6(OH)2(Piv)10(prm)4 (1), which consists of two Mn3 triangular connected by carboxylate bridges. The oxidation of 1 by air led to formation of mixed-valence 1D coordination polymer [MnII2MnIII4(4-O)2(Piv)10(prm)(prm)]n (2). The 2D polymer [Mn4(OH)(Piv)7(prz)2·2MeCN]n (3) was formed in reaction between [Mn(Piv)2(EtOH)]n and pyrazine. Two complexes Mn2(Piv)4( 2-L)2 (L = bpy (4), phen (5)) have been synthesized via the reaction of [Mn(Piv)2(EtOH)]n with stoichiometric amounts of 2,2'-bipyridine or 1,10phenanthroline, respectively, in inert atmosphere. The oxidation of 4 and 5 by air produced tetranuclear mixed-valence complexes MnII2MnIII2(O)2(Piv)6(L)2 (L = bpy (6), phen (7)). The structures of all complexes were determined by single-crystal X-ray diffraction, magnetic properties of complexes 1, 3-5 were studied. Exchange coupling parameters for 3 were calculated by fitting of temperature dependence of magnetic susceptibility and independently estimated by DFT. Acknowledgements - The study was partially supported by joint grant of the National Academy of sciences of Ukraine (No. 10-03-13(U)) and Russian Foundation for Basic Research (No. 12-03-90418), the Council on Grants at the President of Russian Federation (Program for Support of Leading Scientific Schools, NSh2357.2012.3), and Russian Academy of Science. e-mail: i.evstifeev@gmail.com, mkiskin@igic.ras.ru Y10 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NOVEL COORDINATION COMPOUNDS BASED ON OCTAHEDRAL RHENIUM(III) CHALCOCYANIDE CLUSTERS AND COPPER IONS A. Ermolaev, A. Smolentsev and Y. Mironov Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Akademician Lavrentiev Prospekt 3, Novosibirsk, Russian Federation. Compounds containing hexanuclear rhenium(III) cluster anions of the type [Re6(µ3-Q)8L6]n– (Q = S, Se, Te; L = CN, OH and other) have been intensively investigated over the past decade [1]. The long-term interest in hexanuclear rhenium(III) cluster compounds is due to a wide variety of their chemical and physical properties, such as the ability to form many organic-inorganic polymeric structures, redox formations, and luminescence both in solution and in the solid state. Particularly, chalcocyanide anions, containing CN groups as terminal ligands are known as building blocks suitable for the creation of extended arrays of clusters constructed via CN–M–CN bridging, where M is transition 3d-metal. In these compounds, the coordination sphere of the metal centers are often completed by additional ligands such as water or/and ammonia molecules. The addition of chelating ligands can be used to modify the structure dimensionality of the resulting compounds. In this work we present the synthesis and characterization of four compounds containing the [Re6Q8(CN)6]4– cluster anions, CuCN and bpy as chelating ligand (bpy – 2,2’bipyridyl). The novel compounds are the discrete molecular complex [{Cu(bpy)2(µCN)}{Cu(bpy)}2Re6S8(CN)6]·bpy·H2O, 3D polymeric complex [Cu2(bpy)2(CN)][{Cu(bpy)}3Re6S8(CN)6] and 1D polymeric complexes [{Cu2CN(bpy)2}2{Cu(bpy)}4Re6Se8(CN)6] and [{Cu2CN(bpy)2}2{Cu(bpy)}4Re6Te8(CN)6]. All of them were hydrothermally synthesized under autogenous pressure starting from corresponding octahedral rhenium(III) chalcocyanide cluster complexes, CuCN and bpy. It is interesting to note that in the case of [Re6S8(CN)6]4– anion, the variation of reaction conditions leads to the formation of molecular complex (depicted in figure) or 3D coordination polymer. The molecular complex features the presence of differently charged copper ions, Cu+ and Cu2+, possessing tetrahedral and trigonal bipyramidal coordination geometries, respectively. In addition, the compounds were characterized by a set of physical-chemical methods. [1] Y. Kim, V. Fedorov, S.-J. Kim, J. Mater. Chem., 2009, 19, 7178-7190. Acknowledgements - This research was supported by Russian Foundation for Basic Research (Grant No. 11– 03–00157 and Grant No. 12–03–31670– _ ). e-mail: erandrey@yandex.ru Y11 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia BIPYRIDINE AND PHENANTHROLINE IR-SPECTRAL BANDS AS “PROBES” OF METAL SPIN STATE IN HEXACOORDINATED COMPLEXES OF Fe(II), Ni(II) AND Co(II) T. Gerasimovaa and S. Katsyubaa a A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences, 420088, Arbuzov str, 8, Kazan, RUSSIA. Vibrational spectroscopy is often used to observe the influence of the spin state of transition metals on the binding properties of their complexes. A change of the metal spin state affects mostly the bands of metal-ligand stretching vibrations, which are sometimes weak, or overlaid by intra-ligand vibrational modes, or are not unambiguously assignable. The reported applications of mid-IR spectroscopy to analysis of the spin transition behavior are mainly limited to monitoring frequency shifts of easily assignable group characteristic bands, e.g., stretchings of NCS or N3 moieties. Differences in the bands of aromatic ligands occurring with changes of metal spin state are not so pronounced and are therefore difficult to indicate and to interpret. Recently we have demonstrated on the examples of Fe(II) complexes with cyclopentadienyl [1] and tris(pyrazol-1-yl)methane [2] ligands that quantum chemistry is convenient tool for solving this problem and found several bands of the ligands’ vibrations, which are sensitive to the metal spin state. The main limitation of the above approach is the need in rather time-consuming quantum-chemical computations for revealing the mid-IR spectroscopic markers suitable for spin-state diagnostics of every new type of complexes. The analytical power of the method would grow essentially if the markers found for complexes of one transition metal could be applied to studies of similar complexes of other metals. To study such a possibility we simulated quantum-chemically the IR spectra of a series of 2.2’bipyridine (bpy) and 1,10-phenanthroline (phen) complexes of Fe(II), Ni(II) and Co(II) for various spin states of the metals, and compared the computed spectra with the experimental IR spectra of the compounds. Spectral changes caused by variation of metal spin state were found not only for metal-ligand vibrations, but also for the ligands’ modes. Differences between the spectra of bpy and phen complexes with populated and non-populated high-lying 3d-orbitals of the metal were practically independent on the metal nature. This fact allows applying IR markers found for the studied compounds to IR spectroscopic analysis of other complexes of 3d-metals. In particular, the markers revealed were demonstrated to be valid for the bpy and phen complexes of Zn(II) and Cu(II) [3]. This suggests that such widely used ligands as bpy and/or phen can be employed as a sort of versatile IR-spectroscopic “probes” for studies of spin/electronic state of the metal centre in the corresponding complexes. It has been demonstrated very recently by the example of newly synthesized dinuclear complex [Co2(µ-O2P(H)Mes)2(bpy)4]Br2, where Mes = 2,4,6-trimethylphenyl [4]. [1] T.P. Gryaznova, S.A. Katsyuba, V.A. Milyukov and O. G. Sinyashin, J. Organomet. Chem., 2010, 695, 2586–2595. [2] T.P. Griaznova, S.A. Katsyuba, O.G. Shakirova and L.G. Lavrenova, Chem. Phys. Lett., 2010, 495, 50–54. [3] T.P. Gerasimova and S.A. Katsyuba, Dalton Trans., 2013, 42 (5), 1787–1797. [4] E.A. Trofimova, A.B. Dobrynin, T.P. Gerasimova, S.A. Katsyuba, O.G. Sinyashin, D.G. Yakhvarov, Mend. Comm., in press. Acknowledgements - This work was financially supported by the Russian Foundation for Basic Research project 12-03-00483- . e-mail: gryaznovat@iopc.ru, katsyuba@iopc.ru . Y12 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia TRANSITION METAL HETEROMETALLIC COMPLEXES WITH SUBSTETUTED MALONATE ANIONS WITH DIFFERENT METAL RATIO. ASPECTS OF SYNTHESIS AND STRUCTURE FEATURES N.V. Gogoleva, E.N. Zorina, A.G. Zaugolnikova, A.S. Lermontov, M.A. Kiskin, G.G. Aleksandrov, A.A. Sidorov and I.L. Eremenko N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Scinces, 119991, Leninsky prosp., 31, Moscow, RUSSIA. Malonic acid is an efficient bridging ligand for transition metal complexes construction. In literature transition metal heterometallic malonates [MM’(mal)2(H2O)x] are known only with molar ratio M:M’=1:1 and most of that are ionic [1]. In this work we had shown how the complexes packing and metal ratio could be changed. The reaction of CuSO4·5H2O with barium cyclobutane-1,1-dicarboxylate (cbdc2-) and MSO4·6H2O led to crystallization of ionic complexes 2+ 2+ [Cu(cbdc)2(H2O)][M(H2O)6](M=Co (1) or Ni (2)) (Fig. 1, a). With Mn ion complex 4[Cu(cbdc)2(H2O)][Mn(H2O)6][Mn(H2O)8]·15(H2O)·3(H3O) (3) with ratio Cu:Mn=2:1 was crystallized. But when the starting compound was [Cu4K4(Me2mal)8(H2O)8]n (Me2mal2- is dimethylmalonic acid anion) the interaction with M(NO3)2 gave polymers [(H2O)9K2NiCu2(Me2mal)4]n (4) and [( 2 )16K4Co3Cu4(OH)2(Me2mal)8]n (5) (Fig. 1, b) with total Cu:M ratio 2:1 and 4:3 respectively. The another way to change the metal ratio is isomorphic substitution of one transition metal to another. This phenomenon takes place in complex [Co0.6Cu0.4(Me2mal)(H2O)5]n (6), that was obtained in reaction of BaMe2mal with the mixture of CoII and CuII sulfates. a b Fig. 1. Structure of complexes 1 (a), 5 (b). Crystal packing of complexes and the reasons of some or other special features are discussed. [1] Y. Rodriguez-Martin, J. Sanchiz, C. Ruiz-Perez, F. Lloret and M. Julve, Cryst. Eng. Comm., 2002, 4, 631637. Acknowledgements - this study was supported by Russian Foundation of Basic Research (11-03-00735, 12-0331151), The Council on Grants of the President of the Russian Federation (NSh-2357.2012.3), the Russian Academy of Science. e-mail: judiz@rambler.ru Y13 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ACID-BASE PROPERTIES OF DIMETHYLAMINE-BORANE AND ITS COMPLEXES OF TRANSITION METALLS I. E. Goluba, O. A. Filippov and E. S. Shubina a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Street 28, 119991 Moscow, RUSSIA. As hydrogenated amine-boranes R1R2NH–BH3 as well dehydrogenated aminoboranes R1R2N=BH2 – both are of great interest for researchers because of their variety of uses as selective reducing agents and hydroboration reagents in thin organic synthesis, hydrogen source and reversible hydrogen storage material, catalyst of polymerization and building blocks for polymeric materials. The amine-boranes are a neutral equivalent of tetrahydroborate ion (BH4–) and isoelectronic to alkanes, so it can be structural models of activation C–H bonds on metal centers. The dimethylamine-borane (DMAB) and its transition metal complexes was thoroughly studied by means of combination of experimental (IR, UV, NMR and X-ray 190-300 K) and computational (DFT/M06, DFT/BP86) methods. R R R H N R H N L H H H B B B H H H H M H H H H H H H N R R B H L N H R R DMAB contain as acidic center (NH-group) as well as basic center (BH3-group) – so it capable to form a dimer stabilized by dihydrogen bond (DHB). Acid-base interactions are competing with self-association of DMAB depending on the solvent polarity. So it was determined experimentally that in non-polar media (hexane, CCl4) the dominant form is associated with the energy of DHB ΔHH···H= 2.06 kcal/mol, at low-polar media the associated form is 15–30% (with respect to integral intensity of OHfree at 270–290 K) with energy ΔHH···H= 1.47 kcal/mol. From experimental data of interaction organic bases on acidic center and proton donors on basic centers the acidity and basecity factors were determined by Iogansen’s rule of factors and equal to Pi = 0.51 ± 0.06 and Ej = 0.41 ± 0.08 correspondingly. The active intermediates of acid mediated solvolysis were characterized by spectral methods. The crystal products was isolated from reaction mixture and characterized by X-ray. The influence of solvent polarity and its role in ion-pair stabilization was determined by kinetic experiments. On the basis of experimental data by means of quantum-chemical calculations reaction the mechanism was determined and peculiarities of TS structure were revealed. The amine-borane complexes [(PCy3)2IrH2( 2-H2B(H)NRMe2)]+[BAr4F]− (R=H,Me) was synthesized and characterized experimentally. The DHB complexes are revealed by experimental and calculation methods. The thermodynamic characteristic of DHB complexes was determined and active intermediates of proton transfer reaction were identified. [1] A. Staubitz, A. P. M. Robertson, I. Manners, Chem. Rev. 2010, 110, 4079-4124 [2] Y. J. Choi, Y. Xu, W. J. Shaw, E. C. E. Rönnebro, J. Phys. Chem. C 2012, 116, 8349-8358. [3] M. Visseaux, F. Bonnet, Coord. Chem. Rev. 2011, 255, 374-420. [4] V. D. Makhaev, Russ. Chem. Rev. 2003, 72, 257-278. Acknowledgements - This work was supported by Russian Foundation for Basic Research (projects № 12-0331176, 12-03-33018 and 13-03-00604). e-mail: a.seraph347@gmail.com Y14 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia o-BENZOSEMIQUINONATO TIN(IV) COMPLEXES AS THE AGENTS IN THE ELECTRON-TRANSFER REACTIONS E. V. Ilyakina, A. I. Poddel’sky, V. K. Cherkasov and G. A. Abakumov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Electron-transfer reactions play an important role in a variety of chemical and biological processes [1]. Dyads based on the complexes with redox-active ligands and ferrocene are proven as a promising system in terms of electron-transfer interactions. However, nontransition metal complexes based on redox-active ligands have never been noticed in such types of processes. Herein we report on the synthesis and characterization of o-benzosemiquinonato halogencontaining tin(IV) complexes and investigation of their electron-transfer reactions with ferrocenes. Mono-o-benzosemiquinonato halogen-containing tin(IV) complexes were synthesized by the oxidative addition of bromine or iodine to the initial tin(IV) catecholates [2]. The more convenient method of synthesis of bis-o-benzosemiquinonato tin(VI) complexes is the addition of o-benzoquinone to tin(II) halides in acetonitrile [3]. In accordance with electrochemical investigations, o-benzosemiquinonato halogen-containing tin(IV) complexes possess unusually high redox potentials (vs. Cp2Fe/Cp2Fe+, acetonitrile) for such type complexes. This fact indicates that these complexes are able to demonstrate oxidative abilities toward ferrocenes producing ferrocenium salts (Scheme 1). It should be noted that formation of electron-transfer (ET) complexes with ferrocene depends on solvent media. ET complexes obtained in these reactions were characterized by Scheme 1 a variety of physicochemical methods including IR-, EPR-, UV-vis. spectroscopy, X-ray analysis and magnetic measurements. [1] F. A. Armstrong, W. Kaim, B. Schwederski, Bioinorganic Chemistry: Inorganic Chemistry in the Chemistry of Life, Oxford University: Oxford, U. K., 1995; [2] E. V. Ilyakina, A. I. Poddel’sky, A. V. Piskunov, N.V. Somov, Inorg. Chim. Acta, 2012, 380, 57−64. [3] E. V. Ilyakina, A. I. Poddel’sky, A. V. Piskunov, N. V. Somov, G. A. Abakumov, V.K. Cherkasov, Inorg. Chim. Acta, 2013, 394, 282−288. Acknowledgements - We are grateful to RFBR (N 2013-3-01022, 13-03-00891 and 12-03-31367 mol_a), President of Russian Federation (Grants NSh-1113.2012.3), for the financial support of this work. This work was performed according to FSP “Scientific and scientific-pedagogical cadres of innovation Russia” for the years 2009−2013 (N8465 from 31.08.2012). e-mail: ekaterin_from_nn@bk.ru Y15 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia PROTON TRANSFER REACTIONS IN DONOR-ACCEPTOR COMPLEXES OF GROUP 13 METALS TRIHALIDES WITH 2-AMINOPYRIDINE I. Kazakov, A. Timoshkina, M. Bodensteiner and M. Seidlb a Saint-Petersburg State University, Chemistry Department, 148503, Universitetskiy pr, 26, Saint-Petersburg, RUSSIA. b Regensburg University, Chemistry and Pharmacology Department, 93053, University str, 31, Regensburg, GERMANY 2-aminopyridine (aPy) is bidentate nitrogen-donor ligand. It interesting as novel donor for donor-acceptor complexes with group 13 metal trihalides. Potentially this complexes can be a good single-source precursors for chemical vapor depositions of AIIIBV semiconductors and nanomaterials. Useability of this complexes depends of structure and vaporisation processes. The work presented describes synthesis and crystal structures of donor-acceptor complexes with group 13 metal trihalides MX3aPy (M=Al, Ga, In; X=Cl, Br). All synthetic procedures was performed in sealed vacuum systems. X-ray analysis of single crystal was performed for several complexes. In AlCl3aPy, GaCl3aPy, GaBr3aPy found a first example of unusual pyridone-imine (a) structure of 2-aminopyridine, stabilized in crystal structure. H MX3 N NH MX3 N a) NH2 b) As the result, during complexation of 2-aminopyridine with AlX3 and GaX3 proton-transfer reaction from aminogroup to pyridine ring occurs giving piridone-imine structure. Same ligand structure was proposed in work of Dinkov [1] for 2-aminopyridine complexes with Pd (II) found by IR measurements. Metal - nitrogen donor-acceptor bond in AlCl3aPy (1.852Å), GaCl3aPy(1.878Å), GaBr3aPy(1.888Å) is shorter than in typical complexes with nitrogendonor ligands of aluminium trihalides (1.900 - 2.014Å) and gallium trihalides (1.937-2.011Å) [2]. However, 2-aminopyridine in InBr3aPy crystal structure coordinate via nitrogen of pyridine ring with In-N distance 2.182Å. Investigations of vaporization process of GaCl3aPy and InBr3aPy was performed by massspectrometric method. Complexes sublimated at low temperatures (373K) and stable in vapour. [1] Sh. Dinkov, M. Arnaudov, IR- and UV-spectral study on the mechanism of 2-aminopyridine complexation with palladium (II), Spectroscopy Letters, 1998, 31(3), 529-546 [2] E. I. Davydova, T. N. Sevastianova, A. V. Suvorov, A. Y. Timoshkin, Molecular complexes formed by halides of group 4,5,13–15 elements and the thermodynamic characteristics of their vaporization and dissociation found by the static tensimetric method, Coord. Chem. Rev., 2010, 254, 2031 - 2077 Acknowledgements - I. Kazakov is grateful to the DAAD-SPbSU "Dmitriy Mendeleev" scholarship program. A. Timoshkin, I. Kazakov thanks the Saint-Petersburg State University for financial support (12.37.139.2011). e-mail: kazaker@yandex.ru, timoshkn@googlemail.com, michael.bodensteiner@chemie.uni-regensburg.de, michael1.seidl@chemie.uni-regensburg.de Y16 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SOLUTION-DEPOSITED BIAXIALLY TEXTURED LANTHANUM ZIRCONATE AND LANTHANUM HAFNATE FILMS AS BUFFER LAYERS FOR 2G HTS WIRE A. Kharchenkoa, A. Grigorieva, S. Samoilenkovb and A. Kaula,b a Lomonosov Moscow State University, Chemistry Department, Inorganic Chemistry Division, 119991, Leninskie Gory 1/3, Moscow, RUSSIA. b SuperOx, 20-2 Nauchny Proezd, Moscow, 117246 RUSSIA Oxide compounds with pyrochlore structure, La2Zr2O7 and La2Hf2O7, are promising materials for catalytic, optical and electrical applications. Moreover, due to their low lattice mismatch with the YBa2Cu3O7-x high temperature superconductor (~1%) they can be good buffer layers in the architecture of high temperature superconducting tapes [1]. The aim of this work was to develop chemical solution deposition processes to grow La2Zr2O7 and La2Hf2O7 thin films on biaxially textured <001>(001) metal alloy substrates. The coating solutions consisted of a stoichiometric mixture of lanthanum oxide and zirconium or hafnium acetylacetonates dissolved in propionic acid. The advantages of those solutions were their stability at high concentrations and excellent wetting behaviour at metal substrate surfaces. The chemistry of the precursor solutions was studied using thermogravimetric analysis and infrared and NMR spectroscopy. The formation of heteroligand metal carboxylates was found in these complex solutions. The next step was to study the dip coating process of the oxide precursor layer onto continuously moving 80 micron thick Ni-W alloy tapes. There are several important parameters influencing the oxide films thickness and uniformity, namely the solution concentration, viscosity, temperature and speed of tape motion through the solution bath. We quantitatively studied the dependence of the film thickness on the solution concentration and the tape motion rate and found it to correlate well with the predictions of the Landau-Levich theory [2]. Crystalline oxide films of La2Zr2O7 and La2Hf2O7 on the Ni-W tapes up to 10 m long were obtained via high temperature treatment (1000-1150oC) of the precursor-coated tapes under reducing atmosphere in the reel-to reel tape motion mode. X-ray diffraction ( -2 , ω- and φscanning), scanning electron microscopy and electron backscattering diffraction were used for characterization of oxide films. Using the solution deposition approach described we succeeded in preparing biaxially textured La2Zr2O7 and La2Hf2O7 films. The tapes with the La2Zr2O7 films were subsequently used as single buffer layers to make coated conductor tapes with simplified architecture YBa2Cu3O7-x/La2Zr2O7/Ni-5W. The superconducting critical current of over 100 A/cm was measured in the coated conductors obtained. [1] K. Knoth, R. Hühne, and S. Oswald, Thin Sol. Films 2008, 516, 2099-2108. [2] L. Landau, V. Levich, Acta Phisicochim USSR 1942, 17, 42. Acknowledgements This work was supported by the Russian Foundation for Basic Research grant No. 12-03-00754-a and SuperOx company e-mail: kharchenko.andrey@gmail.com Y17 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPLEXES OF YTTRIUM AND LUTETIUM SUPPORTED BY BULKY AMIDO– IMINO LIGAND. SYNTHESIS, STRUCTURE, REACTIVITY AND CATALYTIC ACTIVITY IN ISOPRENE POLYMERIZATION A.A. Kissel, D.M. Lyubov, G.K. Fukin, A.V. Cherkasov and A.A. Trifonov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. 1,4-Disubstituted diazabutadienes attract considerable attention due to their inherent diversity of coordination and redox properties. This ligand system is capable to form fivemembered metallacycles with rigid geometry - promising catalysts for polymerization of lactides, dienes and olefins. A monoanionic amido–imino ligand system [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]− was successfully employed for the synthesis of monomeric dichloro [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]LnCl2(THF)2 (Ln = Y, 1Y; Lu, 1Lu) and bis(alkyl) [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]Ln(CH2SiMe3)2(THF) (Ln = Y, 2Y; Lu, 2Lu) species of yttrium and lutetium. N Cl N Ln + 2LiCH2SiMe3 N hexane, 00C Ln -2LiCl THF THF Cl Ln = Y, 1Y; Lu, 1Lu N THF SiMe3 Me3Si 2Y 75% 2Lu 72% Bis(alkyl) yttrium and lutetium complexes 2Ln activated by AliBu3 and borate (borate = [HNMe2Ph][B(C6F5)4] and [CPh3][B(C6F5)4]; molar ratio 1 : 10 : 1) performed high catalytic activity in isoprene polymerization affording polyisoprenes with predominant 3,4selectivity (up to 78%) and moderate polydispersities (2.14–3.52). The nature of borate was found to affect polyisoprene molecular weight and the 3,4-selectivity of the polymerization reaction, but not the catalytic activity of the ternary catalytic systems. In order to obtain hydride complexes, which are also of interest as a catalyst for the conversion of unsaturated substrates the reaction of dialkyl yttrium complex (2Y) with molecular hydrogen and phenylsilane were investigated. It was established that at the first stage the corresponding hydrido complexes form and undergo further transformations. We found that in the case of reaction of 2Y with H2 Y-C, C-C and C=N bonds of amido-imine ligand undergo hydrogenolysis. This process is accompanied by the redistribution of nitrogencontaining ligands, resulting in the formation of bisligand complex, wherein yttrium atom is coordinated by one diamide ligand with single C-N and C-C bonds and by amido-amine ligand coordinated to the yttrium atom via unusual 3-type due to the amide nitrogen atom and double C=C bond. Acknowledgements - This work has been supported by the Russian Foundation for Basic Research (grant number 11-03-91163- EH_ ; 12-03-31493-a), Program of the Presidium of the Russian Academy of Science (RAS), and RAS Chemistry and Material Science Division. e-mail: okishvegan@mail.ru, trif@iomc.ras.ru Y18 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COORDINATION CHEMISTRY OF KEPLERATES: LIGANDS EXCHANGE INSIDE THE {W72Mo60}-CORE V.S. Koreneva,b a Nikolaev Institute of Inorganic Chemistry Siberian Branch of Russian Academy of Sciences, 630090, Akad. Lavrentyev ave., 3, Novosibirsk, RUSSIA. b Novosibirsk State University, 630090, Pirogova str., 2, Novosibirsk, RUSSIA. Porous spherical oxide-based clusters of the type {(MVI)MVI5}12(linker)30, called keplerates [1], are notable not only for their unique structural features but also because of their properties: they can act as artificial cell membranes exhibiting gated pores while interacting specifically with their environments; they are also of interest for materials science [2-4]. It has been shown that internal surfaces of the keplerates can be used for coordination of different cations and anions. Even encapsulation of a cluster complex inside the cavity based on non-covalent interactions has been achieved, leading to a new type of supramolecular compound. Fig.1. Left. Polyhedral representation of [{W6O21(H2O)6}12{Mo2O4(SeO4)}30]72-. Right. Coordination of selenate-anion to {Mo2O4}2+ bridging fragment. Recently, the mixed-metal keplerate core, {W72Mo60}, containing 12 pentagonal {W6O21(H2O)6} building blocks with 30 internal acetate ligands has been obtained [5]. Herein we report the preparation of three novel keplerate-type structures based on the {W72Mo60}core containing sulfate, hypophosphite and selenate (Fig.1) anions as internal ligands. All new compounds are characterized by X-ray diffraction method, IR, Raman and NMR spectroscopy. It's notable that compound {W72Mo60(SeO4)30} represents the first example of the introducing of selenate anion into the keplerate's cavity. [1] A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, F. Peters, Angew. Chem. Int. Ed., 1998, 37, 3359-3363. [2] N. Hall, Chem. Commun., 2003, 803-806. [3] D.-L. Long, E. Burkholder, L. Cronin, Chem. Soc. Rev., 2007, 36, 105-121. [4] A. Proust, R. Thouvenot, P. Gouzerh, Chem. Commun., 2008, 1837-1852. [5] C. Schäffer, A. Merca, H. Bögge, A.-M. Todea, M.L. Kistler, T. Liu, R. Thouvenot, P. Gouzerh, A. Müller, Angew. Chem. Int. Ed., 2009, 48, 149-153. Acknowledgements to The Ministry of education and science of Russia (project 14.B37.21.1185), to RFBR (project 12-03-31080) and to the grant of the Russian President (project -4318.2013.3). e-mail: wkorenev@niic.nsc.ru Y19 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ACTIVATION OF A (DIENE)RHODIUM(I) COMPLEX SUPPORTED BY A FERROCENYL PHOSPHINE THIOETHER LIGAND FOR HYDROGENATION CATALYSIS : A COMBINED PARAHYDROGEN NMR, UV AND DFT STUDY E. M. Kozinetsa,b, M. Feketec, O. A. Filippova, R. Polib,d, S. B. Duckettc, E. S. Shubinaa, E. Manouryb* and N. V. Belkovaa* a A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilov str, 28, Moscow, RUSSIA. b Laboratoire de Chimie de Coordination du CNRS; Université de Toulouse; UPS, INP; F31077, route de Narbonne, 205, Toulouse, FRANCE; c Department of Chemistry, University of York, YO10 5DD, UNITED KINGDOM d Institut Universitaire de France, 75005, bd Saint-Michel, 103, Paris, France Chiral ferrocene-based phosphine thioether ligands (P,SR) were shown to be particularly efficient for the hydrogenation of aromatic ketones when combined with [Ir(COD)Cl]2 [1]. Since the iridium complexes are too active to generate and characterize the catalytically active species, our attention has turned to the analogous (P,SR)-based rhodium complexes [2], inspired by reports of the isolation and characterization of related diphosphine-based complexes at the pre-catalyst activation stage [3]. These complexes were demonstrated to act as both structural and functional mimics of the analogous Ir systems, although they show lower catalytic activity and selectivity [4]. Scheme 1 Activation of a (diene)rhodium(I) complex with an investigation of the stoichiometric reactivity of these systems towards H2 was studied by parahydrogen NMR, UV and DFT. The addition of H2 to methanol solutions of [Rh(P,SR)(diene)X] (X = Cl or BF4) results in diene hydrogenation with a rate that depends on the structure of the complexes (S atom substituent, nature of the diene ligand and anion). Fast H2/CD3OD exchange on the NMR time scale does not allow the observation of hydride species. However, addition of L (pyridine, acetonitryle) slows down this exchange and allows dihydride products to be observed (Scheme 1). [1] E. Le Roux, R. Malacea, E. Manoury, R. Poli, L. Gonsalvi and M. Peruzzini, Adv. Synth. Catal., 2007, 349, 309-313. [2] E. M. Kozinets, O. Koniev, O. A. Filippov, J.-C. Daran, R. Poli, E. S. Shubina, N. V. Belkova and E. Manoury, Dalton Trans., 2012, 41, 11849-11859. [3] A. Preetz, H. J. Drexler, C. Fischer, Z. Dai, A. Borner, W. Baumann, A. Spannenberg, R. Thede and D. Heller, Chem. Eur. J., 2008, 14, 1445-1451. [4] E. M. Kozinets, G. A. Silantyev, N. V. Belkova, E. S. Shubina, R. Poli and E. Manoury, Russ.Chem. Bull., 2013, 3, in press. Acknowledgements - We thank the CNRS and the RFBR for support through a bilateral project (12-03-93112), the GDRI “Homogeneous Catalysis for Sustainable Development”, and the French Embassy in Moscow for the PhD fellowship of EMK. e-mail: e.m.kozinets@gmail.com Y20 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COORDINATION POLYMERS BASED ON ARYL- AND GETEROARYL(POLI)PHOSPHINIC ACID. SYNTHESIS, STRUCTURE AND PROPERTIES A. Krayushkinaa, V. Milyukova, R. Shekurova, O. Kataevaa and O. Sinyashina a A. E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center of Russian Academy of Sciences, 420088, Arbuzov str, 8, Kazan, RUSSIA. A series of new diphosphinic acids containing aromatic benzene, biphenyl, thiophene bridges between the phosphorus atoms was synthesized and used for the design of coordination polymers of transition metals. Such coordination polymers are of considerable interest in terms of construction new promising materials for storage, purification, separation gas and catalysis. The self-assembly of transition metal ions, which act as coordination centres, linked together with a variety of multidentantny organic ligands (anions of diphosphinic acids above mentioned), has resulted in coordination polymers of different dimensionalities. We studied the effect reaction conditions, and the addition of the bridging ligand on the architecture of the obtained coordination polymers. 1D polymeric chains, 2D polymeric networks and 3D porous coordination polymers of the second generation were prepared. An antiferromagnetic interactions in 1D polymeric chains based on copper, manganese phosphinates were observed. Sorption of 3D porous coordination polymer containing 1,4phenylenebis(phenylphosphinic acid) was measured. [1] S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem. Int. E, 2004, 43, 2334 –2375. [2] K.J. Gagnon, H.P. Perry and A. Clearﬁeld, Chem. Rev. 2012, 112, 1034–1054. [3] B.L. Feringa, R. Hulst, R. Rikers and L. Brandsma, Synthesis, 1988, 04, 316-318. [4] M. Schopferer, G. Schmitt, H. Pritzkow and H.P. Latscha, Zeitschrift für anorganische und allgemeine Chemie, 1988, 564, 121-126. Acknowledgements - We gratefully acknowledge financial support from the Ministry of Education and Science of the Russian Federation (8446). e-mail: krayushkina@iopc.ru Y21 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURE AND PROPERTIES OF NEW COMPLEXES OF 3D-METAL WITH PYRAZOLE-BASED LIGANDS N. Kurnosov Lomonosov Moscow State University, 119991, Leninskie Gory, 1, Moscow, RUSSIA. The aim of this work is the synthesis and study of complexes of 3d-transition elements with N-donor ligands containing pyrazole moiety. 2,6-Bis(pyrazolyl)pyridine and derivatives of 3,6-bis(pyrazolyl)-1,2,4,5-tetrazine are used as ligands. The advantage of these ligands is a possibility of synthesis of large libraries of ligands with different substituents in the pyrazole ring. All used ligands contain at least two heterocyclic rings: relatively easily modifiable pyrazole ring and six-membered heterocyclic ring (pyridine, tetrazine). For the synthesis of ligands may use different methods: synthesis of bisheterocyclic system from a pyrazole derivative, from the derivative of another heterocyclic ring (thiophene, pyridine, tetrazine), or cross-coupling of two heterocyclic rings. Fig. 1. Structures of [Cu(Cl)(bPzPy)]2(ClO4)2 (left) and [Cu(Cl)(bPzPy)(ClO4)] (right). Various symmetric and non-symmetric 2,6-bis(pyrazolyl)pyridines were obtained in a high yield, the yield was highly dependent on the size of the substituents in the pyrazole ring. Synthesized ligands was used for the synthesis of iron, cobalt, nickel and copper complexes. In the case of iron and cobalt complexes of 2,6-bis(pyrazolyl)pyridines have a monomeric structure regardless of counterions and the introduction of additional ligands capable of acting as bridging ligands – halide- and azide- anions. Dimeric complexes with bridging ligands could be obtained for copper and nickel. There is a weak ferromagnetic interaction for dimeric copper complexes with the structure [Cu(Cl)(bPzPy)]2(ClO4)2 (Fig 1.), calculated coupling constant for which is in agreement with the experimental data. Then the introduction of bulky substituents in the pyrazole ring causes distortion of square-planar unit [Cu(Cl)(bPzPy)]2+ and the copper-copper distance increases. For non-substituted pyrazole one-dimensional chain with perchlorate-bridging was obtained in the first time (Fig 1.). Iron and cobalt complexes containing two metal centers were obtained only when using 3,6-bis(pyrazolyl)tetrazine as a bridging ligand. As for copper bis(pyrazolyl)tetrazine undergoes hydrolysis and the hydrolysis products form complexes. Acknowledgements – Author thanks S.I. Troyanov for X-ray data and V.V. Korolev for theoretical calculations. e-mail: nikon.kurnosov@gmail.com Y22 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPLEXES OF COPPER(II) WITH ISOTHIAZOLE DERIVATIVES AND THEIR BIOLOGICAL ACTIVITY E.V. Lider, A.I. Smolentsev Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Acad. Lavrentiev Ave., 3, Novosibirsk, RUSSIA. Complexes of copper(II) with isothiazoles are interesting in view of biological activity of the ligands, which is now under investigation. These azole derivatives may intensify pyrethroid insecticide action against the Colorado potato beetle, and they are known to be very effective. We expect the effect increasing if their copper(II) complexes are used. This work is devoted to new coordination compounds of copper(II) with isothiazole derivatives, their X-ray crystal structure and study of their fungicidal and insecticidal properties. 4,5-Dichloro-N-hydroxy-isothiazole-3-carboxamidine (L1), 4,5-dichloroisothiazole-32 3 carboxylic acid (HL ), its amide (L ) and 3-(4,5-dihlorizotiazol-3-yl)-5-methyl-1,2,4oxadiazole (L4) were chosen as biologically active ligands. Various copper salts with L1 form the following complexes: [Cu(L1)Cl2] (1) and [Cu(L1)Br2] (2). HL2 reacts with copper(II) chloride to form complexes [Cu(H2O)(L2)Cl]·0,5H2O (3), and [Cu(H2O)(L2)2] (4) depending on the ratio metal – ligand. The reaction of different copper(II) salts with L3 and L4 yields in complexes [Cu(L3)Cl2]n (5), [Cu(L3)Br2] (6), [Cu(L3)2(H2O)2](ClO4)2 (7), 3 4 [Cu(L )2(H2O)2](BF4)2 (8), [Cu2(L )2Cl4] (9) (left fig.) and [Cu(L4)Br2] (10) (right fig.). All complexes are investigated by the single-crystal X-ray diffraction. It is shown that all ligands are coordinated in a bidentate-cyclic mode through nitrogen atom of isothiazole ring and one of the oxygen or nitrogen atoms of the substitutes. Fungicidal properties of complexes 3 – 6 in the case of plant pathogenic fungi Botrytis cinerea and Fusarium sp. were investigated. It was shown that all complexes have fungicidal activity and some of them completely suppress fungi pathogenic process. The complexes 4 and 5 were shown to have the highest fungicide activity. Insecticidal properties of the complexes 3 – 6 and 9 – 10 against the Colorado potato beetle larvae (Leptinotarsa decemlineata) as synergist of insecticide “Kerber” were investigated in vitro. It is shown that individual complexes did not cause the death of Colorado potato beetle larvae. A hybrid products Kerber + 6 and Kerber + 10 showed the most effective in the fight against the Colorado potato beetle larvae. Acknowledgements - The work was financially supported by the Russian Foundation for Basic Research (№ 12-03-31343 mol_a). e-mail: lisalider@ngs.ru, smolentsev@ngs.ru Y23 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REACTIONS OF ACENAPHTHENE-1,2-DIIMINE GALLIUM COMPLEXES WITH UNSATURATED COMPOUNDS O.V. Markina, A.N.Lukoyanov, I.L. Fedushkin G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Main group metal complexes with redox-active-diimine ligands attract attention in the last several years. These complexes can reversibly accept and give up electrons thus changing «oxidation state» of the ligands. This feature can be useful in catalytic reactions. Recently we have reported that the binuclear bisamide of gallium complex (dpp-bian)Ga–Ga(dpp-bian) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) may reversibly bind some alkynes and shows a high catalytic activity in reactions of the phenylacetylene with aromatic amines [1]. But we have got no information on addition of unsaturated compounds to mononuclear gallium complexes based on dpp-bian. Here, we report the reactions of (dpp-bian)GaS(S)CNMe2 (1) with organic molecules containing multiple carbon-carbon and carbon-oxygen bonds (Scheme 1). Scheme 1 Reactions of complex 1 with phenylacetylene and 3-buten-2-one afford two complexes [dpp-bian(PhC=CH)]GaS(S)CNMe2 (2) and [dpp-bian(CH2–CH=C(Me)–O)]GaS(S)CNMe2 (3) respectively. In both cases the addition is reversible and starting compound 1 is regenerated by heating the solutions of compounds 2 and 3. Addition of metyl-2-butynoate to 1 proceeds in irreversible manner resulting complex [dpp-bian(CH3–C=C–C(O)–OCH3)]GaS(S)CNMe2 (4). [1] I. L. Fedushkin, A. S. Nikipelov, A. G. Morozov, A. A. Skatova, A. V. Cherkasov, G. A. Abakumov, Chem. Eur. J., 2012, 18, 255-266. Acknowledgements - This work was supported by the RFBR (grant № 12-03-33080). e-mail: omar@iomc.ras.ru, igorfed@iomc.ras.ru Y24 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia MAGNETO/OPTICAL CORE-SHELL GOLD/PRUSSIAN BLUES ANALOGUES NANOPARTICLES Guillaume Maurin-Pasturela, Jérôme Longa, Joulia Larionovaa, Yannick Guaria. a Institut Charles Gerhardt- UMR 5253, EQUIPE CMOS, Université Montpellier II, Place Eugène Bataillon, 34095 Montpellier Cedex5, France. Comparatively to the metal/oxides nanoparticles, the synthesis and the study of Prussian Blue analogues are a relatively recent field in coordination chemistry. These nanoparticles present an interest as on fundamental level for their properties (magnetism, conductivity, selective adsorption). On the other hand, gold nanoparticles present remarkable optical properties because of the plasmon surface phenomena. These nanoparticles are used for a large range of applications, especially in biomedical field (drug delivery vehicles, phototherma therapy, imaging,..). [1] A new concept consists in taking advantage of both optical properties of gold nanoparticles and magnetic properties of Prussian Blue analogues to obtain multifunctional magneto-optical nano-objects. In this regard, hybrid core-shell nanoparticles of Au@KNi[Fe(CN)6] have been synthesized (fig. 1), and show optical properties resulting from plasmon surface band. The formation of a new shell with KNi[Cr(CN)6] by a subsequent growing has permitted to implement successfully magnetic properties. Figure 1: TEM Image TEM of Au@KNi[Fe(CN)6] nanoparticles, on left. On right, Hysteresis cycle of Au@KNi[Fe(CN)6]@ KNi[Fe(CN)6] nanoparticles. [1] Erik C. Dreaden, Alaaldin M. Alkilany, Xiaohua Huang, Catherine J. Murphy et Mostafa A. El-Sayed, Chem. Soc. Rev., 2012, 41, 2740–27 e-mail : Guillaume.maurin02@etud.univ-montp2.fr Y25 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia GENUINE REDOX ISOMERISM IN A RARE-EARTH-METAL COMPLEX A. Morozova, I. Fedushkina, S. Dechertb, S. Demeshkob and F. Meyerb a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b Institut für Anorganische Chemie Georg-August-Universität, 37077, Tammannstrasse 4, Göttingen, GERMANY Redox-isomerism – also called valence tautomerism – in solution and in the solid state is known for various d-elements [1], including Co, Ru, Cr, Ni, Mn, Fe, Rh, Cu, and Ir. Here we report the synthesis and a combined X-ray crystallography plus SQUID study of the new complex [(dpp-bian)Yb(-Cl)(dme)]2 (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), which turns out to be the first rare earth metal complex that exhibits genuine thermally induced redox-isomerism in the solid state. Numerous X-ray diffraction studies of single crystals of 1 isolated from a series of experiments show the presence in every crop of three different modifications, i.e. 1-A (monoclinic P21/n), 1-B (triclinic P-1) and 1-C (triclinic P-1). Unit cell parameters of one of three modifications, namely 1-B, were found to vary significantly with temperature. Ar N Ar O Yb III N O N YbIII Cl Ar Cl O < 150 K O Ar N N Ar Cl YbIII O O Cl N O N > 150 K Ar Ar YbII O N Ar Ar = 2,6-diisopropylphenyl Scheme 1. Redox-isomerism in [(dpp-bian)Yb(-Cl)(dme)]2 (1-B). SQUID measurements of the magnetic susceptibility of a single crystal of modification 1-B showed abrupt increasing of the magnetic moment from 5.2 B at 147 K to 6.6 B at 140 K in cooling mode in the range from 270 to 2 K. Backward scans in heating mode reveal a pronounced thermal hysteresis loop for eff (ΔT = 7 K), until eff returns to the initial value of 5.3 B at 153 K. At the same time modification 1-C demonstrates monotonous decreasing of the magnetic moment with the lowering of the temperature from 295 to 25 K. Figure 1. Plot of eff vs. T for a single crystal of 1-C (solid dots) in comparison to 1-B (open dots). [1] C. G. Pierpont, Coord. Chem. Rev. 2001, 221, 415-433 Acknowledgements – This work was supported by the RFBR (Grant № 13-03-00713) e-mail: morozov@iomc.ras.ru Y26 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE ADDITION OF ALKYNES TO FUNCTIONAL-LABILE BISAMIDES OF ALUMINUM M.V. Moskalev, I.L. Fedushkin G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Complexes of main group metals with redox-active ligands based on -diimines have attracted rising in last years. A major reason for the popularity of these complexes is the idea of the catalytic activation of multiple bonds of organic compounds on these systems. Recently, it was demonstrated that the binuclear bisamide of gallium (dpp-bian)Ga–Ga(dpp-bian), (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), may reversibly bind some alkynes [1, 2], and shows the high catalytic activity in reactions of the phenylacetylene with anilines [2]. Here, we report the reactions of binuclear dialane (dpp-bian)Al–Al(dpp-bian) (1) with various alkynes. Acetylene, phenylacetylene and methylphenylacetylene react with 1 to give cycloaddition products 2, 3 and 4 respectively (Scheme 1). R1 Ar R 2 Ar Ar N N + 2 R1 Ar N R2 N Al Al Al Al N N Ar Ar toluene N Ar 1 1 2 N R 2 Ar R 1 2: R = R = H 3 : R 1 = H, R 2 = Ph 4 : R 1 = CH 3, R 2 = Ph Ar = 2,6-diisopropylphenyl Scheme 1. Reaction of 1 with alkynes. The reactivity of mononuclear ethyl-aluminum derivative (dpp-bian)AlEt(Et2O) (5) towards unsaturated organic molecules also has been investigated. Reactions of complex 5 with diphenylacetylene and methylvinylketone lead to cycloaddition products [dpp-bian(PhC=CPh)]AlEt (6) and [dpp-bian(CH2–CH=C(Me)–O)]AlEt (7). For each case the organic substrate is added across the Al–N–C fragment of metallacycle of starting complex 5. Addition of diphenylacetylene is accomplished with the formation of new C–C and C–Al bonds. The reaction of complex 5 with methylvinylketone (1,3--conjugate) results besides new C–C bond also O–Al bond. Whereas with the methylvinylketone complex 5 readily reacts in toluene at ambient temperature the reaction of 5 with PhC≡CPh does not proceed in solution even at elevated temperatures, for example, in toluene at reflux. However, a placement of 5 in melted diphenylacetylene (110-130 C) allows elimination of the coordinated diethylether molecules and formation of cycloadduct 6. [1] I. L. Fedushkin, A. S. Nikipelov, K. A. Lyssenko, J. Am. Chem. Soc., 2010, 132, 7874–7875. [2] I. L. Fedushkin, A. S. Nikipelov, A. G. Morozov, A. A. Skatova, A. V. Cherkasov, G. A. Abakumov, Chem. Eur. J., 2012, 18, 255-266. Acknowledgements - This work was supported by the RFBR (grants №№ 11-03-01184 and 12-03-33080). e-mail: moskalevmv@iomc.ras.ru, igorfed@iomc.ras.ru Y27 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia EXPANDED RING N-HETEROCYCLIC CARBENES AS SUPER-DONOR LIGANDS. SYNTHESIS, STRUCTURE, APPLICATIONS IN CATALYSIS. Nechaev M. S.ab, Asachenko A. F., Dzhevakov P. B., Morozov O. S., Topchiy M. A., Rubina M. S, and Sorochkina K. R. a Department of Chemistry, Moscow State University, 119991, Leninskie gory 1 (3), Moscow, Russia b A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991, Leninsky prospect 29, Moscow, Russia N-heterocyclic carbenes (NHCs) became widely used as powerful ligands for stabilization of reactive species, as organocatalysts, and as spectator ligands in transition metal catalysis. Most of NHC-metal complexes known to date are derived from five-membered ring imidazol2-ylidene and imidazolin-2-ylidene type carbenes. In recent years our group develops chemistry of 6- and 7-membered ring carbenes. Expanded ring carbenes (er-NHCs) exhibit superior stereoelectronic properties in comparison with five-membered ring counterparts. Expansion of the ring leads to significant increase in donor strength and sterical hindrance. In this contribution we report our recent results on theoretical calculations of electronic structure and ligand properties of er-NHCs; efficient methods of synthesis of precursors and generation of free carbenes; synthesis of late transition metal (Cu, Ag, Au, Pd) complexes. It was found that er-NHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water, and dimerization of terminal alkynes with formation of E-enynes. Cationic gold complexes are active catalysts of indole synthesis in mild conditions. R N NH2 [Au] N H R [Pd] N N TM ( )n [Pd] Ar H e-mail: nechaev@nmr.chem.msu.ru, m.nechaev@ips.ac.ru Y28 + B(OH)2 N Ar Cl Ar International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia METAL-CONTAINING CHLORINS: THE NOVEL TYPE OF PDT-SELECTIVE DELIVERY AGENTS CONJUGATES. A. Nyucheva, K. Shegravina, M. Lopatinb, H.-G. Schmalzc and A. Fedorova a N.I. Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina av., 23, Nizhny Novgorod, RUSSIA. b G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. c Universität zu Köln, 50939, Greinstr. 4, Köln, GERMANY. The novel type of anticancer conjugates for combined photodynamic/chemotherapy and selective delivery to can er cells was developed. Zn-containing chlorin-type compounds [1, 2] were used as PDT agents due to its ability for producing singlet oxygen and fluorescent properties (for bioimaging). 4-Arylaminoquinazolines display properties as vascular endothelial growth factor receptor ligands/epidermal growth factor receptor ligands and tyrosine kinase inhibitor [3, 4], were used as selective delivery agent. Br F HN N O N F + N O O N O HN NH Br O O O Methylpheophorbide a Photodynamic therapy agent HN O O N N O OH O N VEGFR, Selective delivery agent/ chemotherapy agent N N H N N N F Br O N O HN N O NH N O N CO2Me N N O Zn N CO2Me Synthesized compounds display fluorescence in red and infra-red area. [1] E.S. Nyman and P. H. Hynninen, J. Photochem. Photobiol. B: Biology, 2004, 73, 1-28. [2] A.E. O’Connor, W.M. Gallagher and A.T. Byrne, Photochemistry and Photobiology, 2009, 85, 1053-1074. [3] K. Matsuno, J. Ushiki, T. Seishi, M. Ichimura, N. A. Giese, J.-C. Yu, S. Takahashi, S. Oda and Y. Nomoto, J. Med. Chem., 2003, 46, 4910-4925. [4] A. Pandey, D.L. Volkots, J. M. Seroogy, J. W. Rose, J.-C. Yu, J. L. Lambing, A. Hutchaleelaha, S.J. Hollenbach, K.Abe, N.A. Giese and R.M. Scarborough, J. Med. Chem., 2002, 45, 3772-3793. Acknowledgements: DAAD (A/11/74399), Russian Federal Purpose Programme (research projects 16.740.11.0476 and 14.740.12.1382) and RFBR (research project №12-03-00214-а). e-mail: alex.nyuchev@yandex.ru, afnn@rambler.ru Y29 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF HETEROMETALLIC CLUSTERS WITH {Fe2S2} CORE M. Ogienko, S. Konchenko Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090, Acad. Lavrentiev ave, 3, Novosibirsk, RUSSIA. During the last years, the FeS-clusters attract a great attention because of their unique structures and interesting chemical reactivity, and particularly their widespread uses as biomimetic models for the active site of Fe-only hydrogenases. The [Fe2S2(CO)6] (1) cluster is a versatile precursor for synthesis of various heterometallic clusters containing the {Fe2S2} core. This work is focused on the interaction between cluster 1 and diimine complexes of few different metals. The reactions of cluster 1 with [Zn2(dpp-BIAN)2], [Ga2(dpp-BIAN)2] and [Yb(dpp-BIAN)(dme)2] complexes have been observed to lead to reductive cleavage of S–S bond and insertion of corresponding metal into it. The process is accompanying by oxidation of (dpp-BIAN)•– to (dpp-BIAN)0 and Zn+ to Zn2+, or (dpp-BIAN)2– to (dpp-BIAN)•– and M2+ to M3+ (M = Ga, Yb) (Scheme 1). Scheme 1 Acknowledgements - The authors are grateful to the Russian Foundation for basic research (grants No. 12-0331530, 12-03-31759, 13-01-01088), and Federal target program "Kadry" (Contract No. 8631) for financial support. e-mail: ogienkoma@gmail.com, konch@niic.nsc.ru Y30 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NOVEL PARAMAGNETIC TRIANGULAR CLUSTERS OF MOLYBDENUM AND RHENIUM P. Petrova, M. Afonin, G. Sosnin and S. Konchenko a Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, Ak. Lavrentiev Av., 3, Novosibirsk, RUSSIA Previously, we have found that electron-precise clusters [M3Q4(diphos)3Hal3]+ (M = Mo, W; Q = S, Se; Hal = Cl, Br) bearing bulky diphosphane ligands can be easily converted by treatment with gallium metal to paramagnetic clusters with M3Q4, Mo3Q5 or Mo3S4Ga cores [1]. Recently we have found that the reaction of [Mo3S4(dppe)3Br3]Br with GaCp* gives cubane-like cluster [Mo3S4(GaBr)(dppe)3Hal3] with improved yield. The reaction of [Mo3S4(dppe)3Br3]Br with [GaBian]2 leads to a mixture of [Mo3S4(dppe)3Br3] and [Mo3S4(dppe)3Br]Br (Fig. 1; phenyl rings omitted for clarity), i.e., the products of 1- and 2electron reduction of the initial cluster core. In an attempt to obtain the triangular cluster bearing the redox active ligands the reaction of (Et4N)2[Mo3S7Hal6] (Hal = Cl, Br) with potassium 3,6-bis(tert-butyl)catecholate (K2cat) was carried out. The reaction leads to the cluster core destruction, and the mononuclear complex (Et4N)[Mo(cat)3] or the product of its oxidation (Et4N)[Mo(O)(cat)2(Hcat)] were obtained and characterized by means of XRD. The main feature of [Mo(cat)3]– anion (Fig. 2) is the slightly distorted prismatic coordination sphere of Mo(V) ion. Triangular clusters of Re coordinated with diphosphanes were unknown before our work. [Re3S4(dppe)3Br3]+ [2] and [Re3S4(dppe)3(NCS)3]+, in contrast to analogous electron-precise clusters of Mo or W, were found to be paramagnetic with the quartet ground state (S = 3/2). High spin value makes [Re3S4(dppe)3(NCS)3]+ attracting precursor of heterospin arrays or single-molecule magnets. [1] P.A. Petrov, D.Yu. Naumov, R. Llusar et al., Dalton Trans., 2012, 41, 14031-14034. [2] P.A. Petrov, A.V. Virovets, A.S. Bogomyakov et al., Chem. Commun., 2012, 48, 2713–2715. Acknowledgements – The work was supported by RFBR (projects 12-03-31530, 12-03-31759, 12-03-33028, 13-03-01088) and Russian Ministry of Education and Science ('Kadry' task program, contract no. 8631). e-mail: panah@niic.nsc.ru Y31 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia The first non-bent lanthanoidocenes (II) (Ln = Sm, Yb), containing bulky cyclopentadienyl-type ligands. Synthesis, structure and reactivity A.N. Selikhov, A.V. Cherkasov, G.K. Fukin, T.V. Mahrova, A.A. Trifonov a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Structures of sandwich complexes of divalent lanthanides markedly differ from those of metallocene complexes of d-transition metals. Unlike the complexes of d-metals featuring a parallel arrangement of ciclopentadienyl ligands, in the analogues containing Ln(II) the CpM-Cp bond angles are significantly less than 1800, due to the peculiarities of their electronic structure. The purpose of this work is the synthesis of novel complexes of Ln(II) (Ln = Sm, Yb) containing bulky aromatic cyclopentadienyl-type ligands, studies of their structure and reactivity. We investigated the influence of bulkiness of cyclopentadienyl-type ligand on their mutual arrangement in the coordination sphere of Ln(II) ions. Another objective of this research was the synthesis of low-coordinated Ln(II) complexes and investigation of their reactions with ligands non-common for organolathanide chemistry (H2, CO, ethylene, butadiene, SiH4). New biscyclopentadienyl (1) and bisfluorenyl (2) complexes Ln(II) were synthesized by the metathesis reactions of potassium derivatives of corresponding ligands with LnI2 (Ln = Sm, Yb), biscarbazolyl complex of ytterbium was synthesized through reaction of naphthaleneytterbium with 1,3,6,8-tetra-tert-butylcarbazol: 1 2 3 The X-ray diffraction studies revealed that Ln(II) (Ln = Sm, Yb) biscarbazolyl complexes are the first examples of non-bent lanthanoidocenes. e-mail: podriwnik89@yandex.ru Y32 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NOVEL HETEROSPIN RADICAL-ION SALTS OF CHALCOGEN-NITROGEN π-HETEROCYCLES WITH SANDWICH CHROMIUM CATIONS N.A. Semenova, N.A. Pushkarevskyb, E.A. Chulanovac, I.G. Irtegovaa A.S. Bogomyakovd, L.A. Suturinac, N.V. Kuratievab, N.P. Gritsanc, and A.V. Zibareva a N.N. Vorozhtsov Institute of Organic Chemistry of Siberian Branch of the Russian Academy of Sciences, 630090, Lavrentiev Ave., 9, Novosibirsk, RUSSIA b A.V. Nikolaev Institute of Inorganic Chemistry of Siberian Branch of the Russian Academy of Sciences, 630090, Lavrentiev Ave., 3, Novosibirsk, RUSSIA c V.V. Voevodsky Institute of Chemical Kinetics and Combustion of Siberian Branch of the Russian Academy of Sciences, 630090, Rzhanova St., 3, Novosibirsk, RUSSIA d International Tomography Center of Siberian Branch of the Russian Academy of Sciences, 630090, Rzhanova St., 3a, Novosibirsk, RUSSIA Despite fast progress in the design, synthesis and structural and functional characterization of molecule-based magnetic and conductive materials for electronics and spintronics, there is a permanent demand on new building blocks in the field. A big number of candidate building blocks came from chalcogen-nitrogen chemistry especially in the form of neutral and positively charged π-heterocyclic radicals. Investigation of negatively charged chalcogennitrogen π-heterocyclic radicals (i.e. radical anions – RAs) begins only recently. In the present work, compounds 1-3 were reduced with either decamethylchromocene (Cr( 5C5(CH3)5)2, compound 1) or bis(toluene)chromium (Cr( 6-C7H8)2, compounds 1-3) into corresponding RAs, which were isolated in the form of heterospin S1 = 3/2, S2 = 1/2 (4) and S1 = S2 = 1/2 (5-7) radical-ion salts, respectively. Structures of 4, 5 and 6 were elucidated with single-crystal XRD, and a composition of bulk samples was confirmed by elemental analysis. At room temperature, salt 4 is ESR-silent in both the solid state and a MeCN solution. This can be explained by the huge zero-field splitting and fast relaxation of the cation provoking fast relaxation of the anion. ESR spectra of 5-7 in the solid state and DMF solutions confirm their paramagnetic heterospin nature. Magnetic properties (effective magnetic moment eff and magnetic susceptibility χ) for salts 4-7 were measured in temperature range 2-300 K. In all cases magnetic curves are characteristic for antiferromagnetic (AF) coupling of the spins. Approximation of temperature dependencies gives negative values of exchange interactions (Ji) and Weiss constants (Θ) for all salts, with the exception of 6 for which Ji of both signs and small positive Θ are obtained. The latter may be due to contribution of ferromagnetic (FM) interaction in macroscopic properties of 6. Value of eff for the salt 7 at 300 K is characteristic for homospin system with S = 1/2 thus implying diamagnetic π-dimerization of RAs in the solid state. Theoretical values of Ji were calculated on the basis of the XRD structures by a number of quantum-chemical methods to be in a good agreement with the experimental results. Acknowledgements – Authors are grateful to the RFBR (Projects 10-03-00735, 12-03-31759 and 13-03-00072), Presidium of the RAS (Projects 8.14 and 18.17), and Siberian Branch of the RAS (Projects 13 and 105). e-mail: klaus@nioch.nsc.ru Y33 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SINTHESYS, STRUCTURE AND PROPERTIES OF IRON-PHENYLTELLURIUM COMPLEXES S.S. Shapovalova, T.A. Krishtopa, A.S. Sidorenkova, I.V. Skabitskya and A.A. Pasynskya a N.S. Kurnakov Institute of General and Inorganic Chemistry, Leninsky prosp,31, Moscow, 119991, Russia The ability to combine in a single cluster different transitive and intransitive elements in strict predetermined ratio is important in the use of heterometallic complexes as precursors of inorganic and magnetic materials. Heating an equimolar amount of [(5-C5H4(CH3))Fe(CO)2]2 with Te2Ph2 in benzene without boiling affords desired complex (5-C5H4CH3)Fe(CO)2TePh (Ia), which reaction with [(5C5H5)Mn(CO)2(NO)]PF6 leads to the formation of the new compound [(5-C5H4CH3)Fe(CO)2TePh(5-C5H5)Mn(CO)(NO)]PF6 (IIa). If the reaction of (5C5H5))Fe(CO)2TePh (Ib) with PPh3 is carried out in refluxing toluene, formation of the complex (5-C5H5)Fe(CO)(PPh3)TePh (III) take place, which is in the processing of [(5C5H5)Mn(CO)2 (NO)]PF6 in MeCN gives brown crystals of [(5-C5H5)Fe(CO)(PPh3)TePh(5-C5H5)Mn(CO)(NO)]PF6 (IV). We find that (5C5H5)Fe(CO)2TePh (IIb) is rapidly oxidized by FcBF4 or FcBPF6 (Fc – ferrocenium) in CH2Cl2 and complexes [[(5-C5H5)Fe(CO)2]2TePh]+X- (X = BF4 or BPF6, Va,b) are isolated. If the prolonged boiling IIa and IIb is carried out in heptane, formation of the compounds [(5-C5H4CH3)Fe(CO)TePh]2 (VIa) and [(5-C5H5)Fe(CO)TePh]2 (VIb) take place. Oxidation of VIa and VIb and by FcBPF6 result in dimeric paramagnetic complexes formation [(5-C5H4CH3)Fe(CO)TePh]2PF6 and [(5-C5H5)Fe(CO)TePh]2PF6. In case of oxidation of (5-C5H5)Fe(CO)2TePh by FcBPF6 phenyltelluride-bridged complex [{(5C5H5)Fe(CO)2}2TePh]PF6 (VII) can be formed. Treatment of Me3NO to the CH2Cl2 solution of VII followed by addition of on equivalent of (5-C5H5))Fe(CO)2TePh result in threenuclear complex [{(5-C5H5)Fe(CO)2}3{TePh}2]PF6 VIII with two phenyltelluride bridging ligands. + CH 2Cl2 Fe TePh + OC OC + Te Me3NO Fe Fe OC CO OC CO PF 6 Te Te Fe Fe Fe OC CO CO OC CO PF 6vCO = 2026, 2012, 1980, 1969, 1931 cm -1 vCO = 2044, 2022, 1983, 1972 cm -1 Acknowledgements - This work is financially supported by RFBR (grants 09-03-00961, 12-03-33101) and grant of the RF president (MK-7179.2012.3) e-mail: schss@yandex.ru Y34 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia QUANTUM CHEMICAL MODELING OF ADDUCTS OF CO(II) BIS-CHELATES WITH O-BENZOQUINONE LIGANDS: IN SEARCH OF REDOX ISOMERISM A. Starikova, R. Minyaev and V. Minkin Institute of Physical and Organic Chemistry at Southern Federal University, 344090, Stachka Avenue, 194/2, Rostov on Don, RUSSIA. Redox isomerism of coordination compounds (valence tautomerism) is a unique process which consists in reversible intramolecular electron transfer between the ligand and the metal atom excited by external stimuli (temperature, pressure, irradiation and others) [1]. As a rule, valence tautomeric systems contain two redox-active o-benzoquinone ligands with the coordination environment of metal being completed to octahedron by auxiliary ligands. The observed redox-processes in such compounds are associated with transitions between semiquinone and catecholate forms of the ligands. Recently the principal possibility of modeling of another type of valence tautomeric systems has been shown on the example of adducts of bis(N-p-tolylsalycylaldiminato)cobalt(II) with 2,4,6,8-tetra-tret-butylphenoxazin1-one [2]. In this case neutral and radical anion forms of ligand were involved in redoxprocesses. With the aim of extension of the compounds capable of valence tautomerism manifestation the structure and properties of adducts of cobalt ketonates and aminovinylketonates with obenzoquinone and its derivatives, o-benzoquinone imine and o-benzoquinone diimine have been studied using DFT B3LYP*/6-311++G(d,p) method. The influence of substituents on the possibility of occurrence of redox-processes has been studied and valence tautomerism has been predicted for some compounds [3]. [1] E. Evangelio and D. Ruiz-Molina, C.R. Chimie, 2008, 11, 1137-1154. [2] E.P. Ivakhnenko, Yu.V. Koshchienko, P.A. Knyasev, M.S. Korobov, A.V. Chernyshev, K.A. Lysenko and V.I. Minkin, Dokl. Chem., 2011, 438, 155–159. [3] V.I. Minkin, A.A. Starikova and R.M. Minyaev, Dalton Trans., 2013, 42, 1726-1734. Acknowledgements - This work was supported by the Ministry of Education and Science of Russian Federation (agreement No 14.132.21.1466) and Council on Grants of the President of the Russian Federation for State Support of Young Scientists and Leading Scientific Schools (grant No SP-1718.2013.5). e-mail: alstar@ipoc.sfedu.ru Y35 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESES, STRUCTURES AND LUMINESCENT PROPERTIES OF THE LANTHANIDE COMPLEXES CONTAINING 4-HYDROXY-2,1,3BENZOTHIADIAZOLE T. Sukhikha, D. Bashirova, A. Zibarevb, S. Konchenkoa, A. Mustafinac a Nikolaev Institute of Inorganic Chemistry SB RAS, 630090, Acad. Lavrentiev ave, 3, Novosibirsk, RUSSIA b Institute of Organic Chemistry, SB RAS, 630090 Novosibirsk, Acad. Lavrentiev ave, 9, RUSSIA c A.E. Arbuzov Institute of Organic and Physical Chemistry Kazan, 420088, Arbuzov str., 8, Kazan, RUSSIA Lanthanide polynuclear complexes have been attracted increasing interest over last years because they can be used in designing of organic light-emitted diodes (OLEDs), in biomedicine and telecommunication applications [1, 2]. Among them lanthanide complexes containing chalcogen-nitrogen heterocycles and β-diketonates are of especial interest. Herein, we report the syntheses, structures and luminescent properties of the lanthanide complexes containing 4-hydroxy-2,1,3-benzothiadiazole. Ph O O , dbm– = O O Ph S N N N , O-btd– = O O The europium, samarium, erbium and ytterbium complexes of 4-hydroxy-2,1,3benzothiadiazole (OH-btd) and dibenzoylmethane (Hdbm) have been synthesized. It has been shown that the tri- and tetranuclear complexes are formed: [Ln3(dbm)4(O-btd)5] (Ln = Eu, Sm), and [Ln4(dbm)6(O-btd)4(OH)2] (Ln = Er, Yb), [Er4(dbm)4(O-btd)6(OH)2]. Structures of the complexes have been established by single crystal X-Ray diffraction and other routine methods. Furthermore the near infrared luminescence of the compounds has been studied. The emission intensity of [Ln4(dbm)4(O-btd)6(OH)2] having 6 (O-btd)– ligands appears to be higher than those of [Ln4(dbm)6(O-btd)4(OH)2] that have only 4 (O-btd)– ligands. Acknowledgements – The authors are grateful to the Russian Foundation for basic research (grants No. 12-0331530, 12-03-31759, 13-01-01088), and Federal target program "Kadry" (Contract No. 8631) for financial support. [1] H. Suzuki J Photochem Photobiol A: Chem, 2004, 166, 155-161 [2] F. Artizzu et al. Coordination Chemistry Reviews, 2011, 255, 2514-2529 e-mail: tasyha@ngs.ru, konch@niic.nsc.ru Y36 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE COMPLEXES OF TRINUCLEAR MACROCYCLIC COPPER(I) AND SILVER(I) PYRAZOLATES WITH CARBONYL COMPOUNDS A. A. Titov, A. F. Smol’yakov, F. M. Dolgushin, O.A. Filippov and E.S. Shubina A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Russia, 119991, Moscow, V-334, Vavilova Str, 28, Moscow, Russia There is constant interest in the chemistry of coinage metal (group 11 metal) pyrazolate adducts. Cyclic trinuclear complexes of d10 transition metal represent an important class of coordination compounds whose significance spans multiple fundamental areas, such as including acid-base chemistry, metalloaromaticity, metallophilic bonding, supramolecular assemblies, and host/guest chemistry [1, 2]. CF3 F3C N N PhAcFc CF3 N N N Ph2CO M M F3C M N CF3 CF3 M= Ag, Cu The complexation of the copper (I) and silver (I) cyclic trinuclear pyrazolates [ML]3 (M=Cu, Ag; L=3,5-bis(trifluoromethyl)pyrazolate) with acetylferrocene, (phenylacetyl)ferrocene, benzophenone and butanone-2 was studied by means of IR, NMR, UV-vis spectroscopy (230-290K) in low-polar solvents (CH2Cl2, hexane) and X-ray diffraction in solid state. The complexation were observed at all temperature and one type of complexes with coordination of the oxygen atom of CO group to metal atom of [ML]3 were found in solution and solid state. Their spectral features, structure, formation constants and thermodynamic characteristics were determined. Influence of substitutient in pyrazole ring to acid-base properties of macrocycles and complexation will be discussed. [1] Omary, M. A.; Rawashdeh-Omary, M. A.; Gonser, M. W. A.; Elbjeirami, O.; Grimes, T.; Cundari, T. R.; Inorg. Chem. 2005, 44, 8200-8210. [2] Titov A. A.; Filippov, O. A. ; Bilyachenko, A. N. ; Smol’yakov A. F.; Dolgushin F. M.; Belsky, V. K.; Godovikov I. A.; Epstein L. M.; Shubina E. S.; Eur. J. Inorg. Chem. 2012, 5554–5561. Acknowledgements - This work was supported by Russian Foundation for Basic Research (12-03-00872 and 12-03-31176) e-mail: spor4eg@gmail.ru Y37 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COPPER COMPLEXES WITH NEW PYRIDYL-SUBSTITUTED NITROXIDES S. E. Tolstikov, A. S. Bogomyakov, A. Polushkin, G. V. Romanenko, E. V. Tretyakov and V. I. Ovcharenko International Tomography Center, Siberian Branch of Russian Academy of Sciences, 630090, Institutskaya str, 3A, Novosibirsk, RUSSIA. Copper-nitroxide complexes exhibiting thermally-induced magnetic anomalies attract significant attention in the field of molecular magnetism. One of the first of such complexes was tetranuclear complex [(Cu(hfac)2)4LP2]. Its magnetic behavior, similar to spin crossover in the temperature interval 70–140 K, was associated with a transition of the coordinated O atom of the nitroxyl fragment from axial to equatorial position [1]. We synthesized new ligands: LNN bearing, as compared to LP, methyl group in position 4 of the pyridine cycle and LTBN with modified paramagnetic fragment. eff(B.M.) 3,5 3,0 O R N 2,5 N CF3 F3C 2,0 O N LP, R= H LNN, R= Me O Cu O LTBN 1,5 O Cu(hfac)2 NN [Cu(hfac)2L ]2[Cu(hfac)2] CF3 F3C N N O O 1,0 NN [Cu(hfac)2L ]2 [Cu(hfac)2L 0,5 TBN ]2 0,0 0 50 100 150 200 250 300 350 T(K) We succeed in preparation of new Cu(hfac)2 complexes with LNN and LTBN: dimeric complexes [Cu(hfac)2LNN]2 and [Cu(hfac)2LTBN]2, and complex [Cu(hfac)2LNN]2[Cu(hfac)2] with polymer-chain structure. In solid [Cu(hfac)2LTBN]2 antiferromagnetic exchange interactions are realized between paramagnetic centers, while in the complex [Cu(hfac)2LNN]2 in 5–350 K temperature range dominates ferromagnetic exchange. In case of complex [Cu(hfac)2LNN]2[Cu(hfac)2], where cyclic fragments {Cu(hfac)2LNN}2 are linked by Cu(hfac)2 matrixes in chains, there is a drastic increase of µeff at higher temperatures due to the expanded phase transition accompanied by thermochromic effect. [1] F. L. de Panthou , E. Belorizky , R. Calemczuk , D. Luneau, C. Marcenat, E. Ressouche, P. Turek, P. Rey, J. Am. Chem. Soc. 1995, 117, 11247-11253 Acknowledgements - We thank the Council on Grants at the President of the Russian Federation (Program for State Support of Young Scientists, Grants MK-5791.2013.3 and MK-6497.2012.3) and RF Ministry for Education and Science (№ 8436). e-mail: tse@tomo.nsc.ru Y38 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia MIXED-LIGAND BETA-DIKETONATES OF ALKALINE- AND ALKALINEEARTH ELEMENTS: STRUCTURAL FEATURES AND PROPERTIES D. Tsymbarenkoa, A. Makarevicha, N. Kuzminaa a M.V. Lomonosov Moscow State University, 119991, Leninskie gory, 1-3, Moscow, RUSSIA. Interest in the coordination chemistry of alkaline (AE) and alkaline-earth (AEE) elements has increased in the last 20 years. The one of the driving force is the development of new AE and AEE containing materials (superconductiors, ferroelectrics, high-K materials, multiferroics etc.) The metal beta-diketonates and mixed ligand complexes with ancillary donor ligands are the most promising precursors for manufacturing of thin films of these materials. The present work is devoted to novel mixed-ligand complexes of AE and AEE hexafluoroacetylacetonates with polyglymes (CH3O(CH2-CH2O)nCH3, n = 2 – diglyme, 3 – triglyme, 4 – tetraglyme) or trigmo (CH3O(CH2-CH2O)3OH). The DFT calculations predict the formation of M(hfa)(glyme) molecules (M = Na, K; glyme = diglyme, triglyme, tetraglyme) with energy gains of ∆E=110-130 and 75-100 kJ/mol for M=Na and K respectively. The certain compounds were synthesized and their X-ray crystal structures were determined. It was shown that the increasing of the number of donor atoms in polyglyme significantly changes the structure motif and thermal behavior: from 1D polymers [[Na(diglyme)2+][Na7(hfa)8–]]∞ and [[K(diglyme)3+][K2(hfa)3–]]∞ to polynuclear [Na3(hfa)3(triglyme)]2, [Na3(hfa)3(trigmo)2], [Na(hfa)(triglyme)]2, [K4(hfa)4(trigmo)2] and to mononuclear [Na(hfa)(tetraglyme)] [K(hfa)(tetraglyme)] complexes at last. The synthesis of AEE mixed-ligand complexes shows the dependence on synthetic conditions. So, the compounds [Sr(hfa)2(triglyme)] and [Ba2(hfa)4(triglyme)3] could be obtained in anhydrous conditions, while [Ca(hfa)2(diglyme)(H2O)], [Sr(hfa)2(diglyme)(H2O)], [Ba(hfa)2(diglyme)2], [Ca(hfa)2(triglyme)], [Sr(hfa)2(triglyme)(H2O)], [Ba(hfa)2(triglyme)(H2O)] are formed in the presence of water. In contrast to AE compounds the AEE complexes have similar structure motif which does not significantly changes with the increasing the length of polyglyme. However, the intermolecular interactions and thermal behavior correlate with the composition of compounds. The obtained novel complexes of AE and AEE demonstrate high volatility in vacuum and could be recommended as precursors for MOCVD of thin films. Acknowledgements – The supercomputer modeling was performed on SKIF-MSU (Project No. 245). e-mail: tsymbarenko@inorg.chem.msu.ru Y39 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COORDINATION CHEMISTRY APPROACHES TO DESIGN OF NEW LUMINESCENT LANTHANIDE CONTAINING MATERIALS Valentina V. Utochnikovaa, Svetlana V. Eliseeva, Oxana V. Kotova, Leonid S. Lepnev, Alexei G. Vitukhnovsky, Natalia P. Kuzmina a Lomonosov Moscow State University, 119991, Leninskie Gory, 1/3, Moscow, RUSSIA. Thanks to the variable and versatile co-ordination behavior of lanthanide metal ions (LnIII) wide possibilities of the molecular design, by means of combination of different ligands and metal ions in one molecule, are opened. It allows to achieve materials with the required functional properties, including luminescence, varying their composition and structure. Both fundamental and applied tasks of organic luminescent materials can be solved using the coordination chemistry approaches. Understanding of fundamental correlations between luminescent properties, composition and structure of luminescent metal-organic coordination compounds helps to find new highly luminescent materials for common and even special applications. Ten year research in this area, carried out in Laboratory of Coordination Chemistry, Chemistry Department, Lomonosov Moscow State University, resulted in the formation of the Luminescence group, which activity has been aimed on the synthesis along with both structural and luminescent studies and valuation as luminescent materials of coordination compounds of lanthanide ions. Both optically active (Eu, Tb, Dy, Sm, Tm) and optically inactive (Gd, Lu) have been chosen for investigation. In the first group the main task is to find the suitable organic sensitizers of lanthanide luminescence, which will form stable complexes. While in the second group an appropriate metal has to be selected to increase luminescence efficiency or to change luminescent characteristics of emissive organic ligand. Search of the new luminescent materials is carried out among the compounds which are easy to handle and thus can be used for practical applications. Thus great attention has been paid to the methods of compound transformation into luminescent materials and, first of all, into thin films. Among the topics under investigation is a search for the new vis-luminescent materials among lanthanide coordination compounds and their validation as emitting layer materials in OLEDs. To solve the problem of low UV stability of the luminescent lanthanide-organic compounds, the highly stable, but non-volatile and insoluble aromatic carboxylates were suggested, and two new chemical methods of their thin film deposition were proposed and developed. The features of the quenching mechanism of lanthanide coordination compounds is another topic under investigation, aimed on the search of “smart” luminescent sensor materials with temperature-dependent luminescence. Recently the research activity is focused on the quenching mechanism of NIR-emitting lanthanide ions and search for the new higher luminescent compounds. The results of these investigations, the same as the further development in the field of luminescence of coordination compounds, are to be discussed in the presentation. e-mail: valentina.utochnikova@gmail.com Y40 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia EASY WAYS TO FORMATIONS OF THE HOMO- AND HETEROMETALLIC COMPLEXES WITH SEMI-LATERN FRAGMETS M.A. Uvarova, M.A.Golubnichya, I.V.Nefedova, S.E. Nefedov N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky pr,31, Moscow, RUSSIA It was founded that triflates of transition metals (containing very weak anions) where two coordination sites are blocked by molecules of the phenanthroline, reacts in the mild conditions with the donor molecules, such as PhenM(OOCR)2 (M = Cu, Zn, Co, Ni, R = But, Me). Otf R R Otf C N O O M N N C CH2Cl2 M + M' O O C N N O O N M' O C Otf N O N R R Otf Binuclear homo- and heterometallic complexes can be formed as result of this interaction For example the reaction of phenanthroline-copper triflate with PhenCu(OOCR)2 (R = But, Me)(CH2Cl2, r. t.) leads to the formation of binuclear Phen2Cu2( -OOCR)2otf2, with the geometry of the “Chinese semi-latern”. In this complexes two bridging carboxylates ligands supplemented stacking interaction beetwing two coordinated Phen ligands with the delocalized electron density (C...C 3.57). After reaction of this complex with pyrazole or 3,5-dimethylpyrazole, pyrazoles molecules are coordinated in the axial position of the complex, displacing triftat-anions to the outer sphere, and bistrifluoromethylpyrazole are deprotonated with the substitute one of the bridging pivalate anions. Using as the starting complex in this reactions the palladium triflate with PhenM(OOCR)2 (M = Cu, Zn, Co, Ni, R = But, Me) are formed heterometallic complexes with core Pd-Cu, Pd-Zn, Pd -Co, Pd-Ni. The structure of the obtained compounds are discussed by the X-ray data. Acknowledgements- This work was supported by RFBR (projects 11-03-00824, 11-03-01157, 12-0331339) and the Presidium of the Department of Chemistry and Materials Science, Russian Academy of Sciences, and the Council for Grants of the President of the Russian Federation (MK-4452.2013.03) e-mail: snef@igic.ras.ru, yak_marin@mail.ru Y41 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Ni(II) COMPLEXES OF THE NEW PINCER-TYPE LIGANDS PIMCOP, PIM+COP, AND NHCCOP. B. Vabrea, Y. Canacb, R. Chauvinb and D. Zargariana a Université de Montréal, Department of chemistry, H3C 3J7, Edouard-Montpetit blvd, 2900, Montréal, Qc, CANADA. b Laboratoire de Chimie de Coordination (LCC), CNRS 31077, Narbonne Str, 205, Toulouse, FRANCE. Various pincer complexes have found applications in catalysis thanks to their facile synthesis, enhanced thermal stabilities, and novel reactivities. In the past, we have reported on pincer-type complexes featuring phosphinite [1] and imidazolophosphine [2] donor moieties, and recently we have prepared complexes based on new ligands featuring both of these donor moieties. The modular synthesis of the unsymmetrical PimCOP ligands has allowed us to introduce electronic and steric diversity in these ligands, whereas their facile and direct C-H nickellation provides access to new Ni(II) complexes (PimCOP)NiBr. The latter undergo facile N-alkylation to give the imidazoliophosphine-phosphinito complexes (Pim+COP)NiBr, which can further derivatized as follows: ionization at Ni gives the dicationic species [(Pim+COP)Ni(NCMe)]+ whereas reaction with nucleophiles leads to O N N N O Ni(II) the new NHC-phosphinito complexes PR'2 Ni PR2 (PimCOP)NiBr PR2 N PR' 2 (NHCCOP)NiBr [3]. Such postBr PimCHOP synthesis derivatization protocoles of MeOTf the imidazolophosphine moiety in 2OTf PimCOP ligands thus provide rapid O OTf and efficient access to N N PR'2 Ni PR2 unsymmetrical, pincer-type systems O NucN N O N N AgOTf featuring unusual and variable steric Ni PR2 PR'2 Ni PR2 C N NCMe and electronic properties that should R2P(Nuc) Br Me Br be of interest in catalytic applications [(Pim+COP)Ni(NCMe)]+ (NHCCOP)NiBr (Pim+COP)NiBr [4]. We will present the structural, spectroscopic, and electrochemical properties of the title complexes and their catalytic application. [1] (a) V. Pandarus et al. Organometallics 2007, 26, 4321. (b) D. M. Spasyuk et al. Inorg. Chem. 2010, 49, 6203. [2] (a) N. Debono et al. Eur. J. Inorg. Chem. 2008, 2991; (b) I. Abdellah et al. Chem. Asian. J. 2010, 5, 1225. [3] For previous examples of this reaction in the bidentate series see: (a) I. Abdellah et al. Chem. Eur. J. 2010, 16, 13095; (b) I. Abdellah et al. Chem. Eur. J. 2011, 17, 5110; (c) Y. Canac et al. New. J. Chem. 2012, 36, 17; (d) C. Maaliki et al. Chem. Eur. J. 2012, 18, 7705–7714. [4] B. Vabre,; Y. Canac,; C. Duhayon,; R. Chauvin and D. Zargarian, Chem. Comm., 2012, 48, 10446-10 Acknowledgements - Centre National de la Recherche Scientifique (CNRS), ANR program (ANR-08-JCJC0137-01), NSERC of Canada, Centre in Green Chemistry and Catalysis (CGCC). Direction des Relations Internationales of Université de Montréal and Université Paul Sabatier. e-mail: boris.vabre.1@umontreal.ca, yves.canac@lcc-toulouse.fr, chauvin@lcc-toulouse.fr, zargarian.davit@umontreal.ca Y42 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE COMPLEXES OF Ti, Al, Zn BASED ON THE POLYDENTATE LIGANDS: SYNTHESIS, STRUCTURE, APPLICATION IN CATALYSIS K.V. Zaitseva, A.V. Churakovb, I.V. Vasilenkoc, S.V. Kostjukc, S.S. Karlova and G.S. Zaitsevaa a Chemistry Department of M.V. Lomonosov Moscow State University, 119991, Leninskie gory, 1, 3, Moscow, RUSSIA b N.S. Kurnakov General and Inorganic Chemistry Institute of Russian Academy of Sciences, 119991, Leninskii av., Moscow, RUSSIA c Belarusian State University, Physyco-Chemical Problems Research Institute, 220030, Leningradskaya str., 14, Minsk, BYELARUS Materials based on aliphatic polyesters attract much attention due to their biodegradation and biocompatibility. The ring opening polymerization (ROP) using metal complexes as initiators is the most appropriate method for synthesis of such materials due to controlling type of process. The search of new catalysts of this polymerization is the actual task for modern organometallic chemistry. In our work we synthesized and investigated: -1) new complexes of Ti, Al, Zn based on dialkanolamines, pyridine containing alcohols and substituted diethylenetriamines. The complexes of presented type are active initiators of ROP of lactide and -caprolactone. -2) mixed complexes of Al, Zn containing iminophenolate ligands and fragments of functionalized unsaturated alcohols. These compounds were used as catalysts in ring opening polymerization of cyclic lactones. The fragment of unsaturated alcohol is transferred to the end of polymer chain with high level of functionality. This synthetic strategy allows us to obtain macromonomers based on biodegradable materials with high degree of functionalization. Acknowledgements - This work is supported by the RFBR (12-03-00206- , 12-03-90020-Bel_a) and by President Grant for Young Russian Scientists (MD-3634.2012.3). e-mail: zaitsev@org.chem.msu.ru Y43 International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE REACTIONS OF 1,3-DIPOLAR CYCLOADDITION BETWEEN DIFFERENT NITRONES AND STYRENE AND ITS η6-(ARENE)CHROMIUM TRICARBONYL COMPLEXES N. Zarovkina, E. Sazonova and A. Artemov Lobachevsky Nizhny Novgorod State University Of Nizhny Novgorod, 603950, Gagarin Prosp. 23/5, Nizhny Novgorod, RUSSIA. 6- (Arene)chromium tricarbonyl complexes are very interesting reagents for selective organic synthesis. It is related with their typical accepting properties and a large size of chromium tricarbonyl group effectively shielding arene ring. An important field of application of 6(arene)chromium tricarbonyl complexes is the reaction of 1,3-dipolar cycloaddition, also known as a very available and effective method of construction of heterocyclic rings. The reaction proceeds between 1,3-dipoles and unsaturated systems containing multiple bonds. In order to obtain a number of new individual 6-(arene)chromium tricarbonyl complexes of isoxazolidines and to investigate the influence of chromium tricarbonyl moiety on the reaction 1,3-dipolar cycloaddition, we carried out a series of experiments that occur in accordance with scheme: R1 H CH=N R H2C O R2 C R R2 N R2 1 2 4 H N 2 1O 3 3 R1 5 4 5 3 R3 R 1 2 3 1: R1 = Me, R2 = Ph (a) R1 = Me, R2 = Ph[Cr(CO)3] (d) R1 = Ph, R2 = Ph (b) R1 = Ph, R2 = Ph[Cr(CO)3] (e) R1 = But, R2 = Ph (c) R1 = But, R2 = Ph[Cr(CO)3] (f) 1O 3 4 2: R3 = Ph (a) R3 = Ph[Cr(CO)3] (b) The formed derivatives - free and coordinated isoxazolidines 3 and 4 were isolated and characterized by UV, IR and 1H NMR – spectroscopy and X-ray diffraction. Purity of compounds was confirmed by HPLC. It is shown that all the products are 5-substituted isoxazolidines. It is found that the introduction of chromium tricarbonyl group into nitrone or alkene molecule significantly increases the stereoselectivity of the cycloaddition process, increasing the yield of cis-isomer products (table 1). Table 1. The ratio of cis- and trans-isomers isoxazolidines in 1,3-dipolar cycloaddition Nitrone Alkene The ratio of cis- and Nitrone Alkene The ratio of cis- and (1) (2) trans-products (3:4) (1) (2) trans-products (3:4) 1a 2 67:33 1d 2 100:0 1b 2 90:10 1e 2 100:0 1c 2 100:0 1f 2 100:0 1a 2b 83:17 1d 2b 100:0 1b 2b 100:0 1e 2b 100:0 1c 2b 100:0 1f 2b 100:0 Acknowledgements -This work was supported Russian Ministry of Education and Science (“Federal target program of scientific and scientific-pedagogical personnel of innovation of Russia on 2009-2013”) and Russian Foundation for Basic Researches (Proj. 11-03-00074a). e-mail: zarovkinan@mail.ru Y44 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Poster Presentations International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF N-METHYLPYRROLIDINO[70]FULLERENE DERIVATIVES BEARING ORGANIC AND ORGANOMETALLIC SUBSTITUENTS IN 2-POSITION OF A HETEROCYCLIC RING N. Abramova and V. Sokolov A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilova str, 28, Moscow, RUSSIA. In the continuation of our study of the Prato reaction with C60 [1, 2], novel derivatives of Nmethyl[70]fullerenepyrrolidine containing some organic and organometallic residues in position 2 of the pyrrolidine ring have been synthesized. CH3 CH3 N R N R + RCHO + CH3NHCH2COOH + toluene 1a-d 3a-d 2a-d , R= Fe , , Mn(CO)3 a c b d Two isomeric monoadducts were separated by column chromatography in each reaction: cycloadduct at the 1,9 position and 7,8 position of C70. In the course of the Prato reaction between C70 and natural (-) myrtenal, a new chiral centre C-2 arises and, correspondingly, 4 diastereomers are formed. CD spectroscopic studies were carried out for the synthesized optically active compounds 2d, 3d. [1] N. Abramova, S. Peregudova, A. Emel’yanova, A. Pleshkova, V. Sokolov, Russ. Chem. Bull., Int. Ed., 2007, 56, 361-363. [2] N. Abramova, K. Babievski, S. Peregudova, S. Manuylov, V. Sokolov, "Advanced Carbon Nanostructures" (ACN'2011), St.Petersburg, Russia, July 4-8, 2011, 238. Acknowledgements - The work has been supported by Program OKh-1 and Russian Foundation for Basic Research (11-03-00252). e-mail: stemos@ineos.as.ru, sokol@ineos.as.ru P1 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia GOLD(III) "TRICARBOXYLATE" COMPLEXES: SYNTHESIS, SPECTROSCOPY AND QUANTUM-CHEMICAL STUDY N.S. Akhmadullinaa, O.N. Shishilovb, Yu.F. Kargina a A.A. Baikov Institute of Metallurgy and Material Science of Russian Academy of Sciences, 119991, Leninsky pr., 49, Moscow, RUSSIA. b N.S. Kurnakov Institute of general and inorganic chemistry of Russian Academy of Sciences, 119991, Leninsky pr., 31, Moscow, RUSSIA. Binary gold(III) carboxylates are perspective gold-containing compounds, which can be used as precursors for both homogenous and heterogeneous catalysts. However, information about structures and properties of these compounds is still rather limited. It is known, that gold(III) carboxylates can be prepared by change of chloride ligands in AuCl3 by different carboxylate anions [1]. At the same time only gold(III) acetate usage is mentioned in literature, but not any other carboxylates. Also authors noted some traces of decomposition even for justsupplied samples [2]. That makes a development of synthesis and study of properties of binary gold(III) carboxylates be an actual goal of modern chemistry of noble metals. We have prepared a series of gold(III) carboxylates Au(RCO2)3, where R are different in electronic and steric properties (R = Me, CMe3, CF3). We used the following reaction: HAuCl4 + 4RCO2Ag = Au(RCO2)3 + RCO2H + 4AgCl The reaction proceeds in glacial acetic acid (with addition of acetic anhydride) for R = Me or dry acetonitrile for R = CMe3 and CF3. It was shown that gold(III) pivalate (R = CMe3) and trifluoroacetate (R = CF3) can be obtained by change of acetate groups in Au(CH3CO2)3 under 1.5-2-times excess of corresponding carboxylic acids. IR- and NMR-studies of gold(III) carboxylates indicated a presence of two types of carboxylates groups in solid state and in solutions. According to IR-spectroscopic data complexes contain terminal and bridging carboxylate groups in a ratio 1:2. That was confirmed by quantum chemical calculations for structures Au(RCO2)3, Au2(RCO2)6 and Au3(RCO2)9 (R = Me, CF3) (DFT/lanl2dz). Au2( RCO2)6 and Au3( -RCO2)9 structures have lower energy for Au(RCO2)3 unit compare to Au(RCO2)3 itself. Thus one can assume that binary gold(III) carboxylates have nonmonomeric structures. [1] T.E. Nappier, Gold carboxylates and process for preparing the same, Pat. 5210245 USA, C07F 1/12 556/114; 556/115; assignee Mooney Chemicals, Inc. – 852673; filed: 17.03.92; date of patent: 11.05.93. [2] S.D. Bakrania, G.K. Rathore, M.S. Wooldridge, J. Therm. Anal. Calorim., 2009, 95, 117–122. Acknowledgements - We are grateful to the Council of the President of the Russian Federation for young scientists for financial support (project 977.2012.3). e-mail: nakhmadullina@mail.ru. P2 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REACTIONS OF DIETHYLSTANNYLIUM CATIONS ET2SNT+ WITH OXYGENCONTAINING COMPOUNDS A. Alferovaa, T. Kochinab, I. Ignatyeva, V. Avrorina, D.L. Mialochkina a Saint Petersburg State University, 198504, University Ave, 26, Petrodvorets, Saint-Petersburg, RUSSIA b Institute of Silicate Chemistry of Russian Academy of Sciences, 199034, Adm. Makarova emb., 2, Saint-Petersburg, RUSSIA. One of the mostly studied object during the beginning of the XXI century are tricoordinated cations ot the 14th group elements, that are R3M+ (M=Si, Ge, Sn, Pb). This interest is mainly determined by the comparison of their properties and their role as intermediates in chemical processes, as well as their role as catalysts of numerous reactions. The problems of generation of R3M+ cations in the condensed phase resulted in the scarce number of works dealing with their chemical properties. We proposed the use of the nuclearchemical method (NCM) which allows us to generate R3M+ cations and to study their reactions in different aggregate states. The R2TSi+ (R=T, Me, Et, Ph) ions and germylium R2TGe+ ions (R=Me, Et) were studied by this method. In this presentation we report the extension of the NCM to the generation of diethylstannylium cations with oxygen-containing compounds. It was found that the interaction of these catins with alcohols and ethers (BuOH, MeOt-Bu) leads to the formation of stannylation products. In the reaction with alcohol, in contrast to the similar reaction with silylium and germylium cations, stannanol is formed rather than an alkoxyderivative. The plausible reaction mechanisms are proposed based on experimental results and the results of quantum-chemical calculations (B3LYP) of the equilibrium geometries of main isomers in the C4H11Sn+ system and activation barriers for their interconversion. It was found that in the course of ion-molecule reactions cations undergo isomerization with further elimination of hydrocarbons. However, stannylium ions eliminate ethane in contrast to silylium and germylium cations which decompose with elimination of ethane. This fact may be rationalized takimg into account quantum-chemical data which reveal the tendency of stabilization of complexes with alkanes on going from silicon to tin. Experiment and theory both indicate the growing predominance of the other decomposition channel, i.e. homolytic dissociation of the M-C bond on going from Si to Pb. This work was supported by the RFFI grant № 12-03-00383. e-mail: radiochem@yandex.ru, t-kochina@mail.ru P3 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THERMODYNAMIC PROPERTIES OF SOLID SOLUTIONS OF REDOXISOMERIC O-SEMIQUINONIC COBALT COMPLEXES A. Arapovaa, M. Bubnova, N. Skorodumovaa, N. Smirnovab, N. Protasenkoa and G. Abakumova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b Chemistry Research Institute of N.I. Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina av. 23/5,Nizhny Novgorod, RUSSIA. Redox-isomerism phenomenon is of great interest during last three decades due to possible application in molecular devices. o-Semiquinonic complexes of cobalt exhibit a redoxisomerism, i.e. the ability to exist in two forms differing by valent and spin state of metal and ligands. It was shown that the conversion of redox isomers is accompanied by phase transition. Phase transition of o-semiquinonic cobalt complexes with 2,2’-dipyridil (2,2’-bpy)C (3,6DBSQ)2 (1) and 1,10-phenanthroline (1,10-phen)Co(3,6-DBSQ)2 (2) were quantitatively characterized [1, 2]. Complexes 1 and 2 are isomorphous and form solid solutions one in another with any ratio. Each solid solution reveals phase transition which follows redoxisomeric transformation upon temperature change. Thermodynamic parameters of phase transitions depend on the composition of solid solution. The heat capacity of solid solution (1:1) was studied in the range 7–350 K in an adiabatic vacuum calorimeter and the other ones were investigated by differential scanning calorimetry. Resulting diagrams “transition temperature – composition”, “enthalpy – composition” allow us to evaluate the reciprocal influence of isomorphic lattices belonging to different redoxisomeric complexes. [1] B. Lebedev, N. Smirnova, G. Abakumov, V. et al., J.Chem.Thermodynamics, 2002, 34, 2093-2103. [2] M. Bubnov, N. Skorodumova, A. Bogomyakov, et al., Russ.Chem.Bull., Int.Ed., 2011, 60, 440-446. Acknowledgements - We are grateful to the RFBR (grants №№ 13-03-97082, 13-03-97070, 12-03-31367), Russian President Grant supporting Scientific Schools (NSh-1113.2012.3) and Fundamental Research Programm of Presidium of RAS (№ 18) for financial support. e-mail: av_arapova@iomc.ras.ru P4 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia 2,3-DIHYDROXY-4,6-DI-TERT-BUTYL-BENZALDEHYDE - BUILDING-BLOCK FOR SYNTHESIS OF STERICALLY HINDERED CATECHOLES/O-QUINONES M.V. Arsenyeva, S.A. Chesnokova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Last three decades transition metals complexes with redox-active and paramagnetic ligands have studied intensively. These ligands are sterically hindered o-quinones/catecholes, phenols, nitroxyl radicals and other. Progress in organic chemistry of phenols and nitroxyl radicals allow to use these fragment as building-blocks for prepare supramolecular paramagnetic systems. On other hand available building-block for synthesis of stericallyhindered o-quinones/catecholes (with two tert-butyl groups) have not been synthesized up to present. We suggest using 3-hydroxy-4,6-di-tert-butylsalycilyc aldehyde (t-Bu-Sal) as buildind block for sterically-hindered o-quinones/catecholes. This compound has non-typical for stericallyhindered salicylic aldehyde disposition of tert-butyl-groups. It was synthesized from 3,5-ditert-butylcatechol, and can be oxidized to the corresponding o-quinone. t-Bu-Sal is well active in condensation and it was use for synthesis of Shiff-base and hyndrazones, which contain sterically-hindered catechol-fragment. These compounds can be used for further forming sterically-hindered o-quinones or catecholes ligand. Acknowledgements: This work was carried out in the framework of the Federal Target Program “Scientific and Pedagogical Specialists of Innovative Russia for 2009–2013” (Contract GK_8460 from 31.08.2012 and “Target aspirant” agreement N14.132.21.1462 from 01.10.2012), and was financially supported by Russian President Grant supporting scientific schools (NSh-1113.2012.3). e-mail: mars@iomc.ras.ru, sch@iomc.ras.ru P5 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND STRUCTURE OF THE FIRST PHOSPHORYLATED IRON(II) CLATHROCHELATES O.I. Artyushin, I.L Odinets, E.V. Matveeva, A.V. Vologzhanina and Y.Z. Voloshin A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilova str, 28, Moscow, RUSSIA. Up to date, some synthetic pathways to a number of tris-dioximate clatrochelates with encapsulated iron, ruthenium(II) and cobalt(I,II,III) ions, being of the theoretical and practical interests, have been elaborated [1]. However, none of these compounds contained phosphorus-bearing groups, which are the functionalities that could impart both the specific bioactivity and the coordination-chemical properties to the resulting complexes. We have found that an iron(II) dihalogenoclathrochelate readily reacts with (thio)hydrophosphoryl compounds under phase transfer catalysis conditions affording monophosphorylated macrobicyclic complexes 1–3 (Scheme). The reaction rate depends on the acidity of the phosphorylated agent and is substantially higher in the case of the hydrothiophosphoryl compounds. F B O N O N O N F B Cl R2P(X)H Fe2+ N O N O O B F N PTC Cl O N O N O N P N O O B F N O X R Fe2+ N F B R O N O N O N P S Fe2+ R'NH2, X=S N Cl N O O B F N O R=C6H5, X=O (1) R=C6H5, X=S (2) R=OC2H5, X=S (3) NH R' R'= n-C4H9 (4), (CH2)5NH2 (5), 2-CH2Py (6), 2-CH2CH2Py (7) NH2(CH2)5NH2 2 (1 eq.) R'=(CH2)5NH2 R=C6H5, X=S (2 eq.) F B O N O N O N P S Fe2+ N O N O O B F N 8 N H (CH2)5 2 Scheme The reactive chlorine atom of the monophosphorylated iron(II) clatrochelates undergoes nucleophilic substitution with primary and secondary amines as nucleophiles, yielding the corresponding mono- (4–7) and bis-clathrochelates (8), which were characterized using elemental analysis, IR, UV-vis, multinuclear NMR spectroscopy, MALDI-TOF spectrometry and by X-ray crystallography. [1] Y.Z. Voloshin et al., Clathrochelates: synthesis, structure and properties, 2002 ; Angew. Chem. Int. Ed., 2005, 3400; EJIC, 2010, 5401, 2012, 4507 ; Inorg. Chem., 2012, 51, 8362; Dalton Trans. 2012, 746; 921; 6078, 2013, 42, 4373; Chem.Com. 2011, 47, 7737. Acknowledgements. This work was supported by RFBR (grant 12-03-31581). e-mail: matveeva@gmail.com, voloshin@ineos.ac.ru P6 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF HETEROLIGAND LANTHANIDE COMPLEXES BASED ON 3 - (2BENZOTHIAZOLE-2-YL)-2-NAPHTHOL FOR ORGANIC LIGHT-EMITTING DIODES. T. Balashovaa, A. Pushkarev, I. Grishin, G. Fukin and M. Bochkarev a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Recently the main attention has attracted on the application of metal complexes as electroluminescent materials for organic light emitting diodes (OLED). A growing interest has been attracted to the Nd, Er, and Yb derivatives as the efficient materials emitting in nearinfrared regions. The heteroligand ytterbium complexes Yb2(NpSON)4q2 (1) and Yb2q4(NpSON)2 (2) were prepared by the metathetical reactions of Yb[N(SiMe3)2]3 with 3(2-benzothiazol-2-yl)-2-naphthole (HNpSON) and 8-hydroxyquinoline (Hq) in DME (dimethoxyethane) solution. The products were isolated as yellow crystalline powders soluble in DME, THF and MeCN. According to MALDI-TOF mass spectrometry of the reaction afford, besides the desired complexes 1 and 2, two homoleptic byproducts Yb2(NpSON)6 and Yb2q6, which can be separated by crystallisation. The simple three layer devices ITO/TPD/2/BATH/Yb, consisting of ITO on a glass substrate as the anode, N,N/ -bis(3-methylphenyl)-N,N/ -diphenylbenzidine (TPD) as the holetransporting layer, the lanthanide heterocyclic complex as a neat emission layer, 4,7-diphenyl1,10-phenanthroline (BATH) as an electron-transport layer and Yb as the cathode, were fabricated. Figure 1. EL spectra of single layer device ITO/TPD/2/ BATH /Yb. Figure 2. Molecular structures of 3. The EL spectra of 2 exhibited a broad band with maximum at 580 nm originated from NpSON ligand (Fig. 1) and the band at 978 nm is attributed to the 2F5/2 →2F7/2 transition of Yb3+ ion. Difficulties associated with the isolation of the pure desired products, have led to the need to find other methods of synthesis of these compounds. It has been found that the reaction of Cp3Nd with HNpSON in a ratio 1: 2 leads to the formation of complex Cp2Nd2(NpSON)4 (3) (Fig. 2). The Yb analogue Cp2Yb2(NpSON)4 (4) has been prepared similarly. Its reaction with two equivalents of Hq afforded pure complex Yb2(NpSON)4q2 in 66 % yield, which exhibited high metal-centered emission. Acknowledgements - This work was supported by the Russian Foundation of Basic Research (Grants, No. 1303-00097, 13-03-97046) e-mail: petrovsk@iomc.ras.ru P7 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COPPER(I) PYRAZOLONATE COMPLEXES AND COPPER-CONTAINING NORBORNENE BASED COPOLYMERS. SYNTHESIS, CHARACTERIZATION, LUMINESCENT PROPERTIES Yu.P. Barinova, A.I. Ilicheva, E.V. Baranov, V.A. Ilichev, L.N. Bochkarev, G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Pyrazolonate copper(I) complexes were synthesized and fully characterized. The structures of compounds 1 and 2 were determined by X-ray analysis. Ph Ph Ph Ph 1 2 Complex 3 was copolymerized via ring-opening metathesis polymerization with carbazole substituted norbornene monomers. m N Ph N O Ph2P n C O Cu O N Ph2P O 4 m:n = 1:19 Compounds 1-3 were used as emitting materials in organic light-emitting diodes (OLEDs) of the structure ITO/TPD/1-3/BATH/Alq3/Yb. The OLED devices generated electroluminescence of yellow-orange color with maximum brightness of 280 cd/m2. Photoluminescence spectra of polymeric complexes 4 and 5 consist of broad bands attributed to carbazole units (in the region of 370-450 nm), and copper-containing fragments (in the region of 480-560 nm). Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Projects No. 1303-00250_a) e-mail: jully@iomc.ras.ru P8 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia P, S-LIGANDS BASED ON THE THIOPHOPHITES AND THIOPHOPHETANES FOR THE COMPLEXATION WITH I AND VIII GROUP METALS E. Batyevaα, L. Kursheva, N. Yanberdina, E. Zvereva, O. Sinyashin α A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Centre of Russian Academy of Sciences, Arbuzov Str. 8, 420 088, Kazan, RUSSIA To continue our study of bidentate ligands containing P and S donor atoms in complexation with transition metals we synthesized some Cu(I), Ag(I), Au(I), Co(II), Fe(II) complexes based on the P(III)-S- and P(IV)-S-ligands as well: thiophosphites, trialkyltetrathiophosphates (R = i-Pr, Bu), ammonium salts of octathiotetraphosphetane, respectively. The newly synthesized compounds were characterized by elemental analysis, X-ray single crystal diffraction, spectral (IR/Raman, fluorescence, SEM) studies. The P(III),S-ligands, trialkyltrithiophosphites and their derivatives, react with Cu(I) halides to yield 1:1 [metal-ligand] complexes of various structure and coordination modes: the cyclic chain polymeric structure with bidentate type of copper coordination via P and S atoms, which was found to be the most common one for trithiophosphite complexes. The tetrameric cubane structure with monodentate type of metal coordination via P atom for the steric charged P(III),S-ligands and ligands containing P-S-, P-C - bonds. The P(IV)-S-ligands, in particular S=P(SR)3 (R = i-Pr, Bu) have formed 2:1 [metal-ligand] Cu(I) complexes with bidentate coordination of metal via S - atoms both of thiol and thion groups as it was shown by means of the X-ray data. Piperidinium and triethylammonium salts of octathiotetraphosphetane {[P(S)]4(S-HN+R)4}; R=(- H2-)5; (C2H5)3], due to the presence of donor sulfur atoms and cyclic structure comprising the [P4S8]4-anion, act also as P(IV),S-ligands and coordinate the metal ion though all sulfur atoms. The experimental and calculated IR/Raman spectral analysis in the combination with quantum-chemical calculations at DFT level reveals common spectral characteristics corresponding both to Cu(I), Ag(I), Au(I), Fe(II), Co(II) complexes and to P4S84- anion of “free” ligand, the latter is affected by complexation with metal halides being somewhat distored in complexes. This fact demonstrates that the P4S84- moiety is preserved in the structure of complexes regardless of the metal used as well as the conditions of binding of transition metal – ligand, and each sulfur atom is coordinated by metal. Some of the tetraphosphetane derivatives have been identified as promising anti-fungal (Candida albicans) agents whose activity is comparable to that of Amphotericin B, the metal derivatives possessing the fungicidal activity exceeding twice that of original ammonium salts of octathiotetraphosphetane. Acknowledgements – Financial Support of RFBR (№ 12-03-00479) is gratefully acknowledged e-mail:a.batyeva@iopc.knc.ru P9 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Synthesis and structure of the novel silicon and germanium C,O-, O,O- and O,S-chelates based on dimethylamides of 2-hydroxy- and 2-thioacids Yu. I. Baukova, A. G. Shipova, S. Yu. Bylikinb, N.A. Kalashnikovaa, A. A. Korlyukovc, D. E. Arkhipovc, E. P. Kramarovaa and Vad. V. Negrebetskya a N. I. Pirogov Russian National Research Medical University, Department of Chemistry, 1 Ostrovityanova Str., Moscow, 117997, RUSSIA. b The Open University, Department of Life, Health and Chemical Sciences, Walton Hall, Milton Keynes, MK7 6AA, UK c A. N. Nesmeyanov's Institute of Organoelement Compounds of Russian Academy of Sciences, 28 Vavilova Str., Moscow, 119991, RUSSIA. Chelates of hypercoordinated silicon and germanium are well known due to their high reactivity, biological activity, structural diversity and stereodynamic behaviour in solutions. In the present work, we report the synthesis and structures of new cationic Si and Ge complexes containing the fragments of 2-hydroxy- and 2-thioacids. Bischelates 1a,b and 2–3 were synthesised by the reactions of MeSiCl3, t-BuGeCl3 and MeGeBr3, respectively, with two equivalents of corresponding S-trimethylsilyl-N,N-dimethyl2-thioamides. The O-analogues of these complexes, {MeGe[OCHR'C(O)NMe2]2}+Br– • H2O (4, R' = Me, Ph), were prepared in a similar manner. All cationic bischelates were hygroscopic, so in some cases they were isolated as hydrates. In contrast, the corresponding triflates were not sensitive to moisture and could be crystallised in anhydrous form. In particular, a very stable complex {t-BuGe[OCH2C(O)NMe2]2}+ OTf – (5) was prepared by the reaction of t-BuSiCl3, Me3SiOCH2C(O)NMe2 and Me3SiOTf. 1, M = Si, X = Cl, R = Me (a), t-Bu (b), R' = Me 2, M = Ge, X = Cl • H2O, R = t-Bu, R' = H 3, M = Ge, X = Br • H2O, R = Me, R' = H 6, R = H, Me, Ph Cationic complexes 6 containing both C,O- and O,O-chelate ligands were synthesised from equimolar mixtures of MeSiCl3, silylated ligands and Me3SiOTf. These mixed bischelates were particularly stable and could be isolated with good to excellent yields. According to X-ray data, the Si and Ge atoms in compounds 1–6 are pentacoordinate and have coordination environments intermediate between trigonal bipyramid and square pyramid, with two coordinating oxygen atoms in axial positions. Acknowledgements – This work was financially supported by the RFBR (Project Nos. 11-03-00655 and 13-03-01084) in the framework of activity of the Research and Educational Center of RNRMU. e-mail: baukov@rsmu.ru, alex@xrlab.ineos.ac.ru P10 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia MONONUCLEAR GALLIUM COMPLEXES WITH ACENAPHTHENE-1,2DIIMINE LIGANDS: SYNTHES, REACTIONS WITH ALKYNES N. Bazyakina, A. Skatova and I. Fedushkin G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. 1,2-Bis(arilimino)acenaphthene ligands have attracted rising attention in recent years [1]. Recently we have found the reversible addition of alkynes to a (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian - 1,2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene) to give addition products [(dpp-bian)(RC=CR’)Ga-Ga[(R’C=CR(dpp-bian)]. The alkyne adds across the Ga-N-C section, which results in new carbon-carbon and carbon-gallium bonds. The bisgallium complex was found to be a highly effective catalyst for the hydroamination of phenylacetylene with anilines. [2] Here we report the synthesis of monogallium complexes with bis(arylimino)acenaphthene ligands. Reduction of 1,2-bis[(2,6-dimethylphenyl)-imino]acenaphthene (dmp-bian) with gallium metal in toluene leads to bis-ligand gallium compound (dmp-bian)2Ga (1) which containing one radical-anionic ligand and one dianionic ligand. The reaction compound 1 with phenylacetylene affords addition product (dmp-bian)Ga(HC=CPh)(dmp-bian) (2). The phenylacetylene adds across the Ga-N-C section of dianionic ligand which results in new carbon-carbon and carbon-gallium bonds. The reaction 1 with hexyne-1 in the presence of diphenylacetylene leads to formation of complex (dmp-bian)Ga(C≡C-Bu)2 (3) containing radical-anionic dmp-bian ligand. Ph Ar N N Ar H Ar Ar N N Ar Ar Ga N N Ga Ar N N Ar 1 Ar N N Ga Ar H Ph 2 3 Ar = The exchange reaction of [(dpp-bian)Ga(I)]2 with (Me2NCH2CH2)C5H4K of the reagent ratio 1:2 leads to complex (dpp-bian)Ga( 1C5H4(CH2CH2NMe2) (4) in which Cp-ring is connected with gallium by 1-type, and atom of nitrogen coordinates of the metal atom. The compound 4 behave with phenylacetylene with formation of a complex (dpp-bian)Ga(C≡CPh)2 (5). Paramagnetic complexes 1, 2, 3 and 5 have been characterized by EPR- and IR-spectroscopy. Dianion compound 4 have been characterized by 1H NMR-spectroscopy. Molecular structures of 1-5 have been determined by single crystal X-ray analysis. [1] N. Hill, I. Vargas-Baca and A. Cowley, Dalton Trans., 2009, 2, 240-253. [2] I. Fedushkin, A. Nikipelov, A. Morozov, A. Skatova, A. Cherkasov and G Abakumov, Chem. Eur. J., 2012, 18, 255-266. Acknowledgements –This work was supported by Russian Fondation for Basic Research (grant 11-03-01184-a) e-mail: nbt@iomc.ras.ru, skatova@iomc.ras.ru , igorfed@iomc.ras.ru P11 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CYCLOMETALATED PLATINUM(II) COMPLEXES WITH PYRAZOLONATE ANCILLARY LIGAND. SYNTHESIS, CHARACTERIZATION AND LUMINESCENT PROPERTIES Yu.E. Begantsovaa, L.N. Bochkareva, S.Yu. Ketkova, E.V. Baranova and D.G. Yakhvarovb a G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b A.M. Butlerov Institute of Chemistry, Kazan (Volga Region) Federal University, Kremlevskaya str., 18, Kazan, 420008, RUSSIA New cyclometalated platinum(II) complexes with pyrazolonate ancillary ligand were synthesized and structurally characterized. R R R N + K2PtCl4 R EtOCH2CH2OH/H2O N 80 C, 16 h R (Na)pmip, DME N Pt N Cl R O R Pt 80 C, 12 h N O N CH3 CH3 R H3C R = H (1); F (2) Both compounds revealed square-planar geometry. The crystal cell of 1 was found to contain the monomer molecules of platinum compound whereas dimer molecules of 2 with short Pt/Pt contacts of 3.2217(3) A were observed in the crystal cell of 2. Photophysical and electrochemical properties of 1 and 2 were investigated in detail. The highly resolved photoluminesence spectra of the platinum complexes in solution contain emission bands in the region of 470-550 nm attributed to monomer compounds 1 and 2. The triplet-state energies of 1 and 2 obtained from DFT calculations agree very well with the experimental data. In the crystalline state complex 2 revealed excimer emission as a structureless broad band at ca. 584 nm related to dimmer molecules of platinum compound presented in the crystals. Compounds 1 and 2 were used as emissive materials in OLED devices with the structure of ITO/TPD/1 or 2/BATH/Yb. Electroluminescence (EL) of orange color was observed and assigned to eximer emission of platinum complexes. The maximum of brightness of 5300 cd/m2 and current efficiency of 16.47 cd/A were reached. When complexes 1 and 2 were doped into poly-9-vinylcarbozole (1-10 %) color of EL were found to depend on the dopant concentration and changed from green to yellow to white. Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Projects No. 1203-00250- and No. 13-03-00542_a) e-mail: bega@iomc.ras.ru P12 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REDOX PROPERTIES AND ANTIRADICAL ACTIVITY OF NOVEL ORGANOTIN COMPOUNDS WITH HINDERED PHENOL PENDANTS N.T. Berberovaa,b, E.M. Mukhatovaa, V.P. Osipovab, M.N. Kolyadab, Y.A. Grachevac, D.B. Shpakovskyc and E.R. Milaevac a Astrakhan State Technical University, 414056, Tatischeva str, 16e, Astrakhan’, RUSSIA. b Southern Scientific Centre of the RAS, Rostov-on-Don, RUSSIA. c Moscow State Lomonosov University, Moscow, RUSSIA. Organotin complexes with thiol ligands demonstrate the selective cytotoxic activity towards cancer cells [1,2]. The toxicity of organotin compounds is related with the binding of Sn atom with proteins SH-groups as well as with the induced oxidative stress. The hindered 2,6-dialkylphenols are wide used antioxidants in industry and medicine as a models of vitamin E. A series of novel organotin complexes with 2,6-di-tert-butylphenol pendants of general formula RnSn(SR′)4-n: n=2, R′ = 3,5-di-tert-butyl-4-hydroxyphenyl, R = (1); Et (2); Bu (3); Ph (4); R′ (5); n=3, R = Me (6); Ph (7) were synthesized and characterized by NMR, IR and elemental analysis. The oxidation of 1-7 that leads to the relatively stable phenoxyl radicals formation was studied by ESR nd CVA let us to expect the antioxidative activity of complexes. The radical scavenging activity of complexes was monitored by model reaction with stable 2,2-diphenyl-1-picrylhydrazyl radical (DPPH). The antiradical activity of complexes was demonstrated to exceed that of and thiophenol ligand (RSH). Complex 5 (Fig. 1) with four phenol groups was found the most effective radical scavenger (EC50 = 8 ). Fig.1. The molecular structure of R′2Sn(SR′2) (5). The antioxidant properties of complexes were studied in Z-9-octadecenoic (oleic) acid peroxidation. All compounds at 1 concentration were found to decrease the oleic acid hydroperoxides content up to 15 - 20 % (37 oC) and 70 - 80 % (65 oC). Complex 5 was the most active antioxidant. The corresponding diorganotin dichlorides and triorganoton chlorides were inhibitors of peroxidation [2]. Thus, the presence of hindered phenol groups changes the prooxidant activity of organotin scaffold that is eccential for search of new anticancer agents. [1] D.B. Shpakovsky, E.R. Milaeva, et. al., Dalton Trans., 2012, 41, 14568-14582. [2] E.R. Milaeva, V.Yu. Tyurin, D.B. Shpakovsky, O.A. Gerasimova, Zhang Jinwei, Yu.A. Gracheva, Heteroatom Chem., 2006, 17, 475-480. Acknowledgements - The financial support of Federal special-purpose program ”Scientific and scientificpedagogical personnel of innovative Russia” for 2009-2013 (GK-16.740.11.0771) and RFBR (grants № 11-0300389, 11-03-01165, 12-03-00776, 13-03-00487) is gratefully acknowledged. e-mail: berberova@astu.org, vposipova@rambler.ru, milaeva@org.chem.msu.ru P13 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPONENTS OF ADVANCED CERAMIC COMPOSITES BASED ON NANOHAFNIUMCARBOSILANES M. Blokhinaa, G. Shcherbakovaa, D. Zhigalova, V. Shatunova, D. Sidorova, G. Yurkovb. a SSC RF Federal State Unitary Enterprise “State Research Institute for Chemistry and Technology of Organoelement Compounds”, 105118, shosse Entuziastov, 38, Moscow, RUSSIA. b A.A. Baikov’s Institute for Metallurgy and Material Science of Russian Academy of Science, 119991, Leninskiy pr., 49, Moscow, RUSSIA Ceramic metallopoly(oligo)carbosilanes – nanohafniumcarbosilanes are the base for a promising component of composite materials. Nanohafniumcarbosilanes were synthesized by thermal co-condensation of oligocarbosilane (the product of thermal polydimethylsilane rearrangement) and alkyl amide compounds of hafnium. These compounds do not contain harmful for carbide ceramics oxygen and chlorine impurities, are readily soluble in aliphatic and aromatic solvents, under normal conditions have sufficient thermal stability and, at the same time begin to lose their organic framing at a temperature above 140 °C. Energy of D(M - N) bond dissociation is higher than that of D(N - Alk) bond, therefore at the thermal alkyl amide decomposition at first N - Alk bond will be broken, and part of nitrogen may remain in the synthesized polymer. The nitrogen remaining in the polymer plays a positive role, then transforming in nitride ceramic phase, which further contributes to the stabilization of SiC-ceramics. Advantages of ceramic nanohafniumcarbosilanes are: no uncontrolled impurities, high compatibility of the components in the composite, the possibility of microand macro-modeling of ceramics at the stage of ceramic poly(oligo)carbosilane synthesis, and the fabrication of complex geometry nanoceramics without excessively high temperatures and pressure. The presence of refractory metal (Hf) homogeneously distributed in the polymer carbosilane matrix should provide monophasic structure, help to stabilize homogeneous ultrafine ceramics at high temperatures. Nanohafniumcarbosilanes introduction in graphite and silicon carbide ceramics will significantly improve the structure and strength of the products fabricated from these materials (heat-resistant liners, bearings, drilling equipment, special cutting tools, etc.). Acknowledgements – The work was supported by the Russian Foundation for Basic Research (project 13-0312014) e-mail: a.mariya_blokhina@mail.ru, b.gy_yurkov@mail.ru P14 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURES AND MAGNETIC PROPERTIES OF METALCHELATES OF N,O,O(N,O,S) TRIDENTATE SCHIFF BASE PYRAZOLE DERIVED LIGANDS A.S. Burlova, A.I. Uraeva, D.A. Garnovskiia,b, K.A. Lyssenkoc, V.G. Vlasenkod, Y.V. Zubavichuse, V.Yu. Murzine, E.V. Korshunovaa, S.A. Nikolaevskiia, S.I. Levchenkovb, I.S. Vasilchenkoa, V.I. Minkinaa a Institute of Physical and Organic Chemistry of Southern Federal University, Stachki ave. 194/2 Rostov-on-Don, Russian Federation b Southern Scientific Centre of Russian Academy of Sciences, Chekhova ave. 41, Rostov-onDon, Russian Federation c A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilova 28, Moscow, Russian Federation d Research Institute of Physics of Southern Federal University, Stachki ave. 194, Rostov-onDon, Russian Federation e National Research Centre “Kurchatov Institute”, Academician Kurchatov sq. 1, Moscow, Russian Federation The syntheses of a series of novel N,O,O and N,O,S donor tridentate Schiff base ligands via the condensation of 5-hydroxy(mercapto)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with o-hydroxymethylaniline and their Co(II), Ni(II), Cu(II), Fe(III) and Mn(II) complexes are reported. The compounds are characterized by the elemental C, H, N, S analysis, IR spectroscopy; 1H NMR data for ligands, low-temperature magnetic measurements, X-ray absorption spectroscopy. The crystal structures for Ni(II) and Cu(II) coordination compounds with the composition NiL12 and Cu2L12 are established by X-ray crystallography (Fig. 1): b a Fig.1. The general view of binuclear Cu complex (a) and mononuclear Ni complex (b). Depending on the metal center two types of metal-chelates based on N,O,O and (N,O,S) tridentate pyrazole derived Schiff bases were obtained. Mn(II), Co(II) and Ni(II) complexes are characterized by the octahedral environment with an additional coordination of nondeprotonated hydroxy group of o-hydroxymethylaniline moiety, whereas the Cu(II) and Fe(III) ions form 2-oxo bridged binuclear compounds. The copper(II) complex is diamagnetic at room temperature that is consistent with a very strong (2J ~ 1000 cm-1) antiferromagnetic exchange between the two copper centers through the oxygen bridges. The antiferromagnetic exchange interactions between the Fe(III) ions were also observed within a binuclear structure with J = –18.1 cm–1. Acknowledgements We gratefully acknowledge the Russian President Grants (MK-927.2012.3 and MK170.2011.3) and Russian Foundation for Basic Research (grants 12-03-00462, 11-03-00475, 12-03-31285) and Program RAS N 8. e-mail: garn@ipoc.rsu.ru P15 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia AMIDOPHENOLATE AND O-IMINOSEMIQUINOLATE TIN(IV) COMPLEXES M.G. Chegerev, A.V. Piskunov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. In present work we report the synthesis of new various amidophenolate (AP) and oiminosemiquinolate (imSQ) tin complexes. The interaction of sodium o-iminosemiquinolate with organotin chlorides in THF produces paramagnetic compounds with general formula - imSQSnR2Cl (Scheme 1). Scheme 1. The diamagnetic tin compounds APSnR2 were obtained as a result of the reaction between sodium amidophenolate and organotin chlorides in THF (Scheme 2). Scheme 2. Amidophenolate complexes of tin were found to demonstrate redox-activity in reactions with different reagents such as alkyl halides (Scheme 3) or halogens. Scheme 3. Acknowledgements - We are grateful to the FSP ‘‘Scientiﬁc and Scientiﬁc-Pedagogical Cadres of Innovation Russia’’ for 2009–2013 years (GK 8465), Russian Foundation for Basic Research (grant 13-03-97048r_povolzh’e_a), Russian President Grants (NSh-1113.2012.3) for financial support of this work. e-mail: chemax@iomc.ras.ru , pial@iomc.ras.ru P16 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia AMIDINATE COMPLEXES OF YBII/III: FEATURES OF CONFORMATIONAL STRUCTURES A.V. Cherkasov, G.K. Fukin G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. We have carried out X-ray analysis of the molecular and crystal structures of a series of ytterbium amidinate complex which are by derivatives of [{tBuC-(NC6H3-2,6i Pr2)2}YbII( -H)]2 (1) compound: amidinate complexes of YbII - [{tBuC-(NC6H3-2,6i Pr2)2}Yb( -Cl)]2 (2), [{tBuC(NC6H3-2,6-iPr2)2}Yb( -H)( -PPh2)Yb{tBuC(NC6H3-2,6-iPr2)2}] (3), [{tBuC-(NC6H3-2,6-iPr2)2}Yb( -SCH2Ph)]2 (4), YbIII - [{tBuC(NC6H3-2,6-iPr2)2}Yb( SCH2Ph)2]2 (5) and mixed-valence ion-pair YbII/YbIII complex [{tBuC(NC6H3-2,6-iPr+ i i 2)2}Yb(DME2)] [{2,6- Pr2C6H3NC(H)=C(H)NC6H3-2,6- Pr2}2Yb] (6). Complex 1 features a 6 rather unusual κ-N,η -arene type of coordination of amidinate ligand with a surprisingly robust YbII..η6-arene interaction. The X-ray study established that such coordination type is retained in 2-4 complexes. At the same time, one-electron oxidation of the ytterbium center to the trivalent state in 5 and 6 leads to switching of the coordination mode of amidinate ligand from κ-amido,η6-arene to “classical” κ-N,κ-N-chelating. Table 1. G and amidinate ligand G(L)2.28 values in complexes 3-6. 3 Amidinate ligand coordination type G, % G(L)2.28, % 4 κ-N,η6-Ar 90.0(2) 91.7(2) 48.5(2) 49.4(2) 5 6 κ-N,κ-N 91.9(2) 86.9(2) 40.0(2) 37.6(2) G – percentage of the Yb coordination sphere shielded by all ligands, G(L)2.28 – solid angle of amidinate ligand “normalized” to the M-L distance of 2.28 Å. On purpose to analyze relationship between coordination type of amidinate ligand and radii values1 of YbII/III cations (R(YbII) = 1.02 Å, R(YbIII) = 0.868 Å) we have carried out calculation of percentage of the shielded metal coordination sphere in 3-6 complexes by using the method of ligand’s solid angles2. G values in 3-6 complexes lies in the rather wide range 86.9(2)-91.9(2)%. The solid angle G(L)2.28 of the amidinate ligand in 3, 4 is equal to 49% and significantly exceeds of similar characteristic in 5, 6 (39%). Realization of κ-N,κ-Ncoordination mode of amidinate ligand in 3, 4 will lead to unsaturated Yb coordination sphere (G ~ 80%) and kinetic instabillity of complexes. On the contrary, G ~ 100% in 5, 6 will be the result of amidinate ligand coordination by κ-N,η6-arene mode. Such value of G-parameter is too high that lead to instability of these complexes as in 3 and 4. κ-N,κ-N-coordination type in 5, 6 allows to decrease amidinate ligand steric volume and to minimize non-bonded interactions in YbIII coordination sphere. Thus, changing of Yb radii and therefore decreasing of the Yb coordination sphere dimension may be the cause of the amidinate ligand coordination type modification. Results of this study were published3 in “Organometallics”. [1] R.D. Shannon, Acta. Cryst., 1976, A32, 751-767; [2] I.A. Guzei, M. Wendt, Dalton Trans., 2006, 3991-3999; [3] I.V. Basalov, D.M. Lyubov, G.K. Fukin, A.V Cherkasov and A.A. Trifonov, Organometallics, 2013, 32(5), 1507-1516. Acknowledgements: This work was supported by the Russian Foundation for Basic Research (Grant No 12-0331865) and Ministry of Science and Innovations of N. Novgorod region (Grant No 11-03-97030- p), Grant of President of Russian Federation for young scientists (Grant No MK-4908.2012.3, DML), The Ministry of education and science of Russian Federation (project No. 8445). e-mail: ach@iomc.ras.ru P17 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE SYNTHESIS AND THE MEMBRANE-TRANSPORT PROPERTIES OF CHIRAL AMINOPHOSPHONATES AND AMINOPHOSPHINE OXIDES DERIVED FROM NATURAL AMINO ACIDS R. A. Cherkasova, A. R. Garifzyanova, S. A. Koshkina, N.V. Davletshinaa and M.C. Valeevaa O I Kolodiazhnyib and I. O.Yaremchukb a b Kazan (Volga Region) Federal University, A.Butlerov Institute of Chemistry, Kazan,RUSSIA Institute of Bioorganic Chemistry and Petroleum Chemistry NAS of Ukraine, Kyiv,UKRAINE The development of new methods and reagents for the synthesis of organophosphorus analogues of natural compounds represents an important task for synthetic organoelement chemistry. These compounds are interesting as biologically active compounds, as well as lipophilic phosphorylated amines and azopodands that can be used as an effective carriers of the rare metals ions We have synthesized a series of lipophilic α-aminophosphine oxides from the (S)-enantiomers of amino acids using the Kabachnik-Fields reaction in a ternary system: the dioctylphosphineoxide, paraform and the aminoacid hydrochloride. By this procedure we have obtained the enantiomerically pure bis- and monomethylphosphinylated derivatives of alanine, valine, leucine, serine, threonine, glutamic and aspartic acids respectively in good yield (above 87%). Also, we have synthesized (SP,R)-diastereomers of phosphinylated amino acids by introducing to the reaction system of the (RP)-phenyldecylphosphine oxide. The reaction leads to the inversion of configuration at the phosphorus atom and to the formation of (SP,R)-diastereomers of phosphorylated amino acids. For the obtained compounds membrane transport properties in relation to glycine, alanine, valine, leucine, serine and aspartic acids were studied. The rate of transfer is strongly influenced by the steric volume of the substituent on the α-carbon atom of the substrate as well as the carrier. The steric hindrance reduces the stability of the membrane-transport complex, therefore valine worse transferred through the membrane by all the studied compounds than glycine, alanine and leucine. We have developed the method for the preparation of phospha--homoproline and phosphonic analog of glutamic acid. The synthesis of phosphahomoproline was developed staring from natural L-proline, which was converted to the N-Boc-prolinal, then to the hydroxyphosphonate as a (S,S)+(S,R) diastereomeric mixture of 2:1 ratio. Deoxygenation of hydroxyphosphonate by means of Barton-McCombie method leads to the formation of the protected phosphahomoproline. The depropection and acid hydrolysis of the latter provide the phosphahomoproline, which was isolated as an optically pure solid. The synthesis of phosphonic analog of glutamic acid was developed starting from the tbutyl N-t-butoxycarbonylaspartate. The carboxy-group of this compound was reduced with sodium borohydride in methanol giving the t-butyl-(S)-N-(t-butoxycarbonyl)homoserine. The latter was converted into the bromide by the Appel reaction Then the bromide was introduced into the Arbuzov reaction with (EtO)2POSiMe3 to yield phosphonate, deprotection of which with diluted hydrochloric acid resulted in the phosphorus analog of glutamic acid. This work was supported by RFBR (13-0390448-a) and SFBR of Ukraine (Ф53.3/016 ) grant programs. e-mail: a. rafael.cherkasov@ksu.ru P18 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NEW POLYNUCLEAR Cu(I) CHELATES OF THE THIOUREA-BASED LIGANDS R.A. Cherkasov,a T.R. Gimadiev, a L.N. Yamalieva,a D.B. Krivolapov,b I.A. Litvinov,b D.R. Chubukaeva, a and F.D. Sokolov a a Kazan (Volga Region) Federal University, A.Butlerov Institute of Chemistry, Kazan, Russia b Arbuzov Institute of Organic and Physical Chemistry, Kazan, Russia Polynuclear complexes of d10-metal cations are of interest due to their photophysical behavior and catalytic properties. They were successfully used as precursors to the nanolayers and nanoparticles of the metals and metal chalcogenides. We synthesized and studied the new family of Cu(I) complexes based on the ligands of general formula R (S)NHP(S)(R`)2 (HL), were R = PhNH, morpholyn-N-yl, i-PrNH, t-BuNH; R` = OBu-i, OEt. New polynuclear Cu(I) chelates of formulas [CunLn] and [Cu6(L)6·2CuI)] were obtained. Their structure were characterized by ESI mass-spectrometry and IR, NMR 1H and 31P spectroscopy. A new polynuclear CuI mixed-ligand complex [Cu6(L)6·2CuI)] (L = [iPrNHC(S)NP(S)(OEt)2-S,S`]-) has been structurally and spectroscopically characterized. It has a cage-like structure formed by two [Cu3L3] cycles interconnected by four S-Cu-S bridges. Comparison of the obtained and literature data gave the new information about influence of the structures of R and R` (substituents in HL) on the structure of the obtained polynuclear chelates. We suggest that relatively small steric volume of the PhNH and i-PrNH substituents and their ability to H-bonding can promote formation of the large polycyclic [CunLn] aggregates with n > 4. On the contrary, steric hindrance caused by the bulky substituents, e.g. morpholyn-N-yl, makes the further association impossible. Thus, the aggregation process stops at the simple trimetric (n = 3) or tetrameric (n =4) molecules formation. This work was supported by RFBR (12-03-00474-а) grant program. e-mail: a. rafael.cherkasov@ksu.ru P19 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia OPTICALLY CONTROLLED SYNTHESIS OF THE METAL-CONTAINING POLYMERS BASED ON -QUINONEMETHACRYLATES M.P. Shuryginaa, M.V. Arsenyeva, N.Yu. Shusunovaa, S.A. Chesnokova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. An optically controlled synthesis of the metal-containing polymers based on quinonemethacrylates was elaborated. For this purpose, studies on the synthesis of monomeric quinonemethacrylates, their polymerization and copolymerization with mono- and dimethacrylic monomers, photochemical transformation of o-quinones fragments in monomers and polymers, revelation of optimal condition for photo-formation of metalcontaining polymers with a specified distribution of metal concentrations were performed. Quinonemethacrylates were synthesized in two ways: methacrylation of 2-hydroxy-3,6-ditert-butyl-p-benzoquinone by methacryloyl chloride with alkali and alkoxylation of 3,6-ditert-butyl-o-benzoquinone by monomethacrylic glycol ethers. New monomers polymerization allowed synthesis of polymers with o-quinone group in each link of polymer chain. It was found that the most active monomer in the bulk polymerization is o-quinone based on ethylene glycol monomethacrylate (QMEG). Polymers containing potassium, copper, thallium, manganese and antimony complexes were synthesized from poly-oquinonemethacrylate by reaction with metal (K, Cu, Tl), photolysis (Mn2(CO)10), metathesis with Cu(I) complex and oxidative addition (SbPh3). Addition of metal-framefork to quinone-containing polymers allows synthesis of metal-containing polymers with specified molecular weight characteristics of quinone-containing polymers. Also synthesis of antimonycontaining polymer was realized in-situ by polymerization of o-quinonemethacrylate solution in the presence of SbPh3 (oligomeric products, ~10 link). Investigation of kinetics of buthylacrylates (BA) and buthylmethacrylates (BMA) polymerization in the presence of QMEG (initiator was AIBN, 70 ) demonstrated, that QMEG forms copolymers with BA and BMA and shows properties of weak inhibitor and chain transmitter. Performed spectrophotometric studies showed -quinone fragment of QMEG and poly-QMEG to be reduced efficiently to catechol by visible light in both solution and polymeric film. Either QMEG or amines (N,N-dimethylaniline, N,N-dimethylcyclohexylamine) can serve as a donor of hydrogen. Two methods of selective metal addition to quinone-polymeric layers were studied. The first way was creating of complexes on exposed surfaces of polymer. In this area quinone was reduced to catechols adsorbing the metal ions from water solution accompanied with the metal complexes formation in the films. The dependence of the metal complexes concentration in the layer on exposure is S-shaped. This way was released using Mo, V and Fe salts. The second way was creating of complexes at non-exposed area by the reaction of oxidative addition of metal-fragments and -quinone. This method was demonstrated using SbPh3. Treatment of polymer films in THF solution with SbPh3 leads to oxidative addition of SbPh3 to polymer at non-exposed area. These antimony containing polymers are capable to reversibly join molecular oxygen many times. Acknowledgements: This work was supported by Russian President Grant supporting scientific schools (NSh-1113.2012.3) and by the Russian Foundation for Basic Research (grant no 12-03-01092- , 13-03-97064_ ) e-mail: sch@iomc.ras.ru P20 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia PROBLEMS OF C–H BONDS ACTIVATION IN 1,10-PHENANTHROLINES IN NON-DEHYDROGENATIVE CH–CH COUPLING BY IONS OF d-ELEMENTS IN THE SYNTHESIS OF BIOACTIVE σH-1,10-PHENANTHROCYANINE COMPLEXES V. Demidova,b, T. Pakhomovac, N. Kasyanenkoa a St.-Petersburg State University, Physical Department, 198504, Ulyanovskaya str., 3, Peterhof; bConcern Pro-breit, 196084, Zastavskaya str., 31/2, St.-Petersburg, RUSSIA; c St.-Petersburg State Institute of Technology (Technical University), 190013, Moscowsky pr., 26, St.-Petersburg, RUSSIA. Species of C–H bonds activation in electron-deficient 1,10-phenanthrolines in direct nondehydrogenative isohypse CH–CH coupling (SNH or SET) by ions of d-elements in the synthesis of the new class apocyanine chromophores-fluorophores – electron-rich σH-1,10phenanthrocyanines of d-elements as novel anion receptors, DNA complexones, potential photosensitizers or photocatalysts of singlet oxygen O2 (S1) or superoxide-anions O2─• and hydroxide-radicals •OH generation in DNA visible light photodamage, potent biocides (potential inductors of oxidative stress), potential antitumor agents and inductors of apoptosis have been considered. Results of the investigation of C–H bonds activation in 1,10-phenanthrolines: N N N H3C N CH3 3 in direct non-dehydrogenative isohypse metal-assisted (d –Cr(III), d5 –Mn(II), d6 –Rh(III), d7 –Co(II), d8 –Ni(II), Pd(II), Pt(II), d10 –Zn(II), Cd(II)) CH–CH coupling reactions inclusive of nucleophilic substitution of hydrogen SNH (addition (Add), anion control) or single electron transfer (SET, from a reducing agent to a 1,10-phenanthroline complex) stages in the synthesis of the new class chromophores-fluorophores – glassy (solid phase) or hemicolloidal (in solutions) bioactive electron-rich homobinuclear bridget σH-1,10phenanthrocyanines: [LmMn+( -N,N–N’,N’-phencyanines)Mn+Lm]z+ ( -N,N–N’,N’-phencyanines = -phencyanine, z+ = 2n+ or ( -phencyanine)─, z+ = (2n1)+) containing π-conjugated (quasiheteroaromatic) tautomeric dihydro-bi-1,10phenanthroline ligand systems ( -N,N–N’,N’-phencyanines) [1, 2] are presented. Intensive optical excitation of 1,10-phenanthrocyanine complexes in visible region (450 – 580 nm) relates with -1,10-phenanthrocyanine ligand-centered π→π*-electron transitions: [LmMn+( -phencyanines)Mn+Lm]2n+ + h → [LmMn+( -phencyanines)*Mn+Lm]2n+. Electron-rich complexes in solutions to associative binding with anions, including DNA are inclined. New compounds have antibacterial, antiviral and antitumor properties stronger (on order and more) than their 1,10-phenanthroline complex precursors. [1] V. Demidov, S. Simanova, A. Savinova et al., Ross. Khim. Zhurn. (Russian J. Chem.), 2009, 53, 128-134. [2] V. Demidov, N. Kasyanenko, V. Antonov et al., Ross. Khim. Zhurn. (Russian J. Chem.), 2010, 54, 120-135. Acknowledgements – authors are thankful to RFFI for financial support. e-mail: vnd-inct@mail.ru, pakhom@list.ru P21 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia POLYMERIZATION OF STYRENE AND METHYL METHACRYLATE IN THE PRESENCE OF MONOCATHECHOLATE COMPLEXES OF TIN(IV) A. Dorodnisynaa, L. Vaganovaa, A. Maleevab, A. Piskunovb and D. Grishina a Nizhny Novgorod State University, 603950, Gagarin av, 23/5, Nizhny Novgorod, RUSSIA. b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Bis-catecholate complexes of germanium(IV) and tin(IV) reversibly reacts with macroradicals and therefore can be used as a chain growth regulator in polymerization of different vinyl monomers [1]. The aim of our work was to investigate the influence of mono-catecholate complexes of tin(IV) on polymerization of styrene (St) and methyl methacrylate (MMA) initiated by azobis(isobutyronitrile) (AIBN) at 70°C. Complexes 1-3 were studied in this processes. But O Sn R2 THF O t Bu there R = Me (1), Et (2) or Ph (3) It was shown that introduction of each of the complexes 1-3 leads to a decrease of the St polymerization rate. The maximum yield of polySt at a ratio of complex / AIBN = 1 / 1 is ~ 50-60%. The presence of these metallocomplexes providing a linear growth of MW polySt with conversion. In case of MMA the role of these catecholates of tin(IV) depends on their composition. Complex 1 has no effect on either rate of MMA polymerization or molecular weight characteristics polyMMA at 70°C regardless of the concentration. The presence of 3 at a ratio of 3 / AIBN = 2 / 1 reduces the rate of polymerization of MMA and providing a proportional growth of MW polyMMA. The MMA polymerization rate with 2 extremely dependent on its concentration. Increasing the 2 / AIBN ratio leads to a change in the form of curves of molecular weight distribution (MWD). In case of 2 / AIBN = 2 there is a bimodal MWD and the share of high-molecular modes increases with conversion. Formation of the o-semiquinone complexes of tin(IV) in monomers for each of 1-3 was proved by the ESR method. At the initial stage of St polymerization with 1-3 and synthesis of polyMMA in the presence of 3 fixed five-coordinate o-semiquinones. The paramagnetic derivatives of 1-2 in MMA is six-coordinate and containing in its structure the molecule of monomer. Thus, the ability of complexes tin(IV) to act as a chain growth regulator defined of its composition and structure of the respective paramagnetic derivatives. [1]. Vaganova, L.B., Maleeva, A.V., Piskunov, A.V., and Grishin, D.F., Izv. Akad. Nauk, Ser. Khim., 2011, №8, P.1594–1601. Acknowledgements - This work was supported by the Russian Foundation for Basis Research (project no. 11– 03–00674). e-mail: dorodnicyna.anastasiya@mail.ru P22 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia POLYNUCLEAR CYMANTRENECARBOXYLATES CONTAINING LnIII AND MnII P.S. Koroteeva, N.N. Efimova, A.B. Ilyukhina, A.S. Bogomyakovb, Zh.V. Dobrokhotovaa, V.M. Novotortseva a N. S. Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, RUSSIA. b International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3a, 630090 Novosibirsk, RUSSIA. Carboxylate derivatives of stable organometallic molecules are perspective building blocks for construction of polynuclear 3d-4f-heterometallic complexes which are able to combine specific properties of an organometallic moiety and a rare earth ion. Until recently mostly the derivatives of ferrocene (see references in [1-3]) were known. Lately we have obtained and studied 3d-4f-carboxylates containing the cyclopentadienyltricarbonylmanganese (cymantrene) moiety, the ions of cerium group lanthanides and THF [1], pyridine [2] or DMSO [3] as neutral ligands. On a basis of yttrium group Ln3+ ions and cymantrenecarboxylic acid CymCO2H (Cym = ( 5C5H4)Mn(CO)3)) new 3d-4f-heterometallic clusters [LnIII2MnII2( 3-OH)2( 2O2CCym)8(THF)2] (Ln = Dy (1), Ho (2), Er (3), Yb (4)), having analogous «defect dicubane» structure of the metal core (Fig. 1), trinuclear centrosymmetric [ErIII2MnII( 2-O2CCym)6( 2ym)2((MeO)3PO)4].2MePh (5) and cationic tetranuclear [TbIII4( 32 OH)4(O2CCym)6(H2O)3(THF)4][MnIICl4]·4CH2Cl2·6THF (6) were obtained and characterized by X-ray analysis. Mn2+ ions appear in the structures due to photolytic destruction of the cymantrenecarboxylate moiety in the solution. Magnetic properties of the complexes are indicative of ferromagnetic exchange interactions between the paramagnetic ions in cases of 1 and 5 (Fig. 2); in case of 6 antiferromagnetic interactions prevail. Thermal decay of 1 - 4 was studied by means of DSC and TGA techniques, the products of thermolysis in air according to X-ray powder diffraction data contain LnMn2O5 phases, some of which exhibit the properties of multiferroics.  cm K/mol 3 50 40 30 0 50 100 150 200 250 300 T Fig. 2. Magnetism of 1 (■) and 5 (▲). Fig. 1. Molecular structure of 1 - 4. [1] P.S. Koroteev, M.A. Kiskin, Zh.V. Dobrokhotova et al, Polyhedron, 2011, 30, 2523–2529. [2] P.S. Koroteev, Zh.V. Dobrokhotova, M.A. Kiskin, A.S.Lermontov et al, Polyhedron, 2012, 43, 36–46. [3] P.S. Koroteev, Zh.V. Dobrokhotova, A.B. Ilyukhin et al, Russ. Chem. Bull., 2012, 61 (6), 1069-1078. This study was financially supported by the RFBR (project nos. 11-03-00644, 11-03-00556, 12-03-31395), the Council on Grants of the President of the Russian Federation (grants, NSh-1670.2012.3, SP-6585.2013.5), the Ministry for Education and Science of the Russian Federation (SC-8437) e-mail: nnefimov@narod.ru, pskoroteev@list.ru P23 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia STRUCTURE, MAGNETIC BEHAVIOR AND THERMOLYSIS OF NEW RARE EARTH FERROCENECARBOXYLATES P.S. Koroteev, N.N. Efimov, A.B.Ilyukhin, Zh.V. Dobrokhotova, V.M. Novotortsev N. S. Kurnakov Institute General and Inorganic Chemistry Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, RUSSIA. Discovered in the middle of the last century, ferrocene, in addition to many other interesting properties, is a potential building block for construction of heterometallic complexes. Organometallic compounds containing Fe as a part of the ferrocene fragment and another metal in the ionic form, represent a peculiar type of heterometallic complexes as they are able to combine the specific properties of ferrocene and the properties of the second metal [1,2]. New rare earth ferrocenecarboxylate complexes, [Ln2( - , 2-O2CFc)2( 2- , ′-O2CFc)2( 2NO3)2(DMSO)4] (Ln = Gd (1), Tb (2), Y (3)) and [Gd2( - , 2-O2CFc)2( 2O2CFc)4(DMSO)2(H2O)2]·2DMSO·2CH2Cl2 (4), were prepared and characterized by X-ray analysis. In contrast to all the previously known rare earth ferrocenecarboxylates (e.g., [3]), in structures of 1-3 the Ln3+ ions are connected by four bridging carboxylates (two of them are chelate-bridging; Fig. 1), but complex 4 has “traditional” structure with two chelate-bridging carboxylates. Coordination number of Ln3+ in 1 - 4 is 9. Thermolysis of 1 – 3 was studied by means of DSC and TGA techniques. The final products of thermolysis both under air and in inert atmosphere contain the garnets Ln3Fe5O12 which are valuable magnetic materials, the perovskites LnFeO3, and Fe2O3 in different ratios. Magnetic properties of 2 are indicative of distinct ferromagnetic interactions between the Tb3+ ions (Fig. 2). Weak aniferromagnetic (JGd-Gd' = -0.03979±0.00253 cm-1) and ferromagnetic (JGd-Gd' = 0.02179±0.00285 cm-1) interactions were found in complexes 1 and 4 respectively. cm K/mol 3 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 0 Fig. 1. The molecular structure of 1 - 3. 100 200 300 T, K Fig. 2. Magnetism of 2. [1] W.R. Cullen, J.D. Woollins, Coord. Chem. Rev., 1981, 39, 1-30. [2] P.I. Gaponik, A.I. Lesnikovich, Yu.G. Orlik, Russ. Chem. Rev., 1983, 168-184. [3] Guo Dong, Li Yu-ting, Duan Chun-ying, Mo Hong, Meng Qing-jin, Inorg. Chem., 2003, 42, 2519-2530. This study was financially supported by the RFBR (project nos. 11-03-00644, 11-03-00556, 12-03-31395), the Council on Grants of the President of the Russian Federation (grants, NSh-1670.2012.3, SP-6585.2013.5), the Ministry for Education and Science of the Russian Federation (SC-8437) e-mail: nnefimov@narod.ru, pskoroteev@list.ru P24 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia BOND LENGTHS IN ORGANOMETALLIC COMPLEXES AND POLARIZABILITY EFFECT A.N. Egorochkin, O.V. Kuznetsova, and N.M. Khamaletdinova G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Str., 603950 Nizhny Novgorod, RUSSIA The literature data on X substituents influence on the bond lengths d have been analyzed for 11 narrow series of complexes XCNAg+ (AgN, DFT [1]), X2GeCH4 (GeC, DFT [2]), X2GeH2C=CH2 (GeC, DFT [3]), X2Cl2Snphen (phen=1,10-phenanthroline, SnN, X-ray [4]), (SiO, X-ray [5]), (GeN, DFT [6]), Me O X3Si XGe(OCH2CH2)3N N CHMePh XSn(OCH2CH2)3N (SnN, DFT [6]), XPb(OCH2CH2)3N (PbN, DFT [6]), X2Sn(SCH2CH2)2O (SnO, X-ray [7]), ( X C O )2SbPh3 (SbO, X-ray [8]), and ( X C O )2BiPh3 (BiO, X-ray [9]). O O The distinctive feature of these narrow series is such that for each of them the indicator centre (bond Ag–N, Ge–C, Sn–N, etc.) remains fixed whereas the substituents X vary. Therefore these series are well suited for the study of substituents effects on d, using the correlation analysis. With this method, we have obtained a number of equations which relate the d values with the inductive I, resonance R (R+, R), polarizability , and steric Es’ parameters of X substituents. For all narrow series the best fitting correlation equations are of the form d = d0 + aI + bR(R+, R) + c + kEs’ These equations are distinguished from the other possible ones by their highest adjusted correlation coefficients and the smallest standard errors of approximation. Besides, all coefficients (a, b, c, k) of these equations are statistically significant. This is strong proof that the bond lengths d depend on the joint influence of the inductive, resonance, polarizability, and steric effects of substituents. The reason for the occurrence of the polarizability effect (an ion-dipole interaction between the charge q and the dipole moment induced by q in the substituent X) is the appearance of an excess charge q on the atoms of the test bond as a result of the charge transfer from the donor centre of the complex to the acceptor one. Thus it is impossible to obtain a clear knowledge of substituent influence on the bond lengths in organometallic complexes without considering the polarizability effect. [1] T. Shoeib et al., J. Phys. Chem. A, 2001, 105, 710-719. [2] M. D. Su, S.Y. Chu, J. Am. Chem. Soc., 1999, 121, 4229-4237. [3] M. D. Su, S.Y. Chu, J. Am. Chem. Soc., 1999, 121, 11478-11485. [4] M.A. Buntine et al., Z. Kristallogr., 1998, 213, 669-678. [5] V.V. Negrebetsky et al., Russ. Chem. Rev., 2009, 78, 21-51. [6] S.S. Karlov et al., J. Mol. Str. (THEOCHEM), 2005, 724, 31-37. [7] Yu.I. Baukov, S.N. Tandura, in: Z. Rappoport (Ed.) The Chemistry of Organic Germanium, Tin and Lead Compounds. Wiley, Chichester, 2002, p. 963. [8] V.V. Sharutin et al., Russ. J. Coord. Chem., 2003, 29, 780-789. [9] I.V. Egorova et al., Russ. J. Coord. Chem., 2006, 32, 644-651. e-mail: egor@iomc.ras.ru P25 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND COORDINATION PROPERTIES OF NOVEL LIGAND CONTAINING PHENOL AND DIAZABUTADIEN FRAGMENTS E. N. Egorova, N. O. Druzhkov and G. A. Abakumov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. N-(1-(5,7-di-tert-butyl-2-methyl-2,3-dihydrobenzo[d]oxazol-2-yl)ethylidene)-2,6diisopropylaniline 1 was obtained by condensation of 2-amino-4,6-di-tert-butylphenol with αiminoketone 2. It has been found that compound 1 undergoes ring open process to form enamine species of ligand. It has been shown that the selective deuteration of methyl group at the imine carbon atom takes place in methanol solution. The oxidation of compound 1 with alkaline solution of potassium ferricyanide leads to substituted benzoxazine 3. Coordination properties of ligand 1 were investigated. The reaction of 1 and zinc or cadmium iodide results in neutral complexes (4, 5). The addition of methyl derivatives of group 12 and 13 metals (Me2Cd and Me3M, M=Al, Ga, Tl respectively) in diethyl either solution to an equimolar solution of 1 results in formation of the crystalline thallium, aluminium, gallium and cadmium phenolate compounds 6-9. Compound 1, 3-9 were characterized by NMR spectroscopy. The structure of compound 1, 4, 6, 8, 9 were confirmed by the data of X-ray analysis. Acknowledgements - This work was supported by the Program for support of Leading Scientific Schools (NSh 1113.2012.3), the Russian Foundation for Basic Research (12–03–31348_mol_a and 13-03-97103r_povolj'e_a), and the Ministry of Education and Science of the Russian Federation (the Federal Target Program “Scientific and Scientific-Pedagogical Personnel of the Innovative Russia in 2009–2013,” State Contract no. 8465). e-mail: elen.egorova2009@yandex.ru P26 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia AMIDOPHENOLATE GALLIUM(III) COMPLEXES IN REDOX TRANSFORMATIONS I. Ershova, A. Piskunov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Amidophenolate gallium(III) complexes reactivity towards various oxidizers was investigated. It was observed that the main products of oxidation reactions of [APGaX]2 are five-coordinated bis-iminobenzosemiquinolate gallium(III) complexes with the general formula imSQ2GaX (X = Me, Cl, Br, I). These compounds form as a result of disproportionation of intermediate monoradical four-coordinated complexes. The interaction between [AP2Ga]Na.2THF and allyl halides leads to the allyl fragment addition to the both of amidophenolate ligand rings. The migration of allyl substitute was found to proceed under heating conditions in the All-AP2GaHal complexes. The EPR-spectra of these reaction mixtures belong to the monoradical gallium(III) complexes imSQGa(Hal)All. As mentioned above such type compounds appear to undergo symmetrization to produce biradical complexes imSQ2GaX (X = Cl, Br, I). Acknowledgements - We are grateful to the FSP ‘‘Scientiﬁc and Scientiﬁc-Pedagogical Cadres of Innovation Russia’’ for 2009–2013 years (GK 8465), Russian Foundation for Basic Research (grant 13-03-97048r_povolzh’e_a), Russian President Grants (NSh-1113.2012.3) for financial support of this work. e-mail: irina@iomc.ras.ru, pial@iomc.ras.ru P27 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CRYSTALS OF CU(II) COMPLEX WITH NITRONYL- AND IMINONITROXIDE EXHIBITING MECHANICAL ACTIVITY S. V. Fokina, E. V. Tretyakov, E. Yu. Fursova, O. V. Kuznetsova, G. V. Romanenko and V. I. Ovcharenko a International Tomography Center, Siberian Division of Russian Academy of Sciences, 630090, Institutskaya Str, 3 , Novosibirsk, RUSSIA. Previously, it was shown that deoxygenation of L in crystals of heterospin complexes [Cu(hfac)2L2], where hfac is hexafluoroacetylacetonate anion, L is 2-(N-methyl-1H-imidazol5-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyle, accompanied by a specific mechanical behavior of crystals – jumps and various movements [1]. In course of our study of multispin compounds exhibiting a chemomechanical activity, we synthesized and investigated a series of new heterospin solids [Cu(hfac)2LxL12-x], [Cu(hfac)2L1], [Cu2(Piv)4L12].0.5C6H14, [Cu2(hfac)2(Piv)2L12], where L1 is 2-(N-methyl-1H-imidazol-5-yl)-4,4,5,5-tetramethyl-2imidazoline-1-oxyle, Piv is 2,2-dimethylpropionate anion. It was shown that only solid solutions [Cu(hfac)2LxL12-x] crystals (where L predominates, 1.728  x < 2) had packing similar to [Cu(hfac)2L2] and able to chemomechanical activity. On the contrary, [Cu(hfac)2LxL12-x] crystals (where L1 predominates, 0 < x  0.708) possessed structural characteristics similar to [Cu(hfac)2L12] and did not show any thermo- or photoactivated chemomechanical activity, because of [Cu(hfac)2L2] and [Cu(hfac)2L12] belong to different groups of symmetry, they could not form a continuous series of solid solutions and flowing solid phase process [Cu(hfac)2L2](s) → [Cu(hfac)2L12](s) + O2(g) should cause the tension in the "original" structure and its subsequent destruction. L1 L [Cu(hfac)2L12] [Cu(hfac)2L2] [1] V. I. Ovcharenko, S. V. Fokin, E. Yu. Fursova, O. V. Kuznetsova, E. V. Tretyakov, G. V. Romanenko, A. S. Bogomyakov, Inorg. Chem., 2011, 50, 4307. Acknowledgements. We are grateful to the Ministry of education and science of Russian Federation (projects 8436 and 14.132.21.1451), the Russian Foundation for Basic Research (grants nos. 12-03-00067, 12-03-31184, 12-03-00010), Presidium of the Siberian Branch and Russian Academy of Sciences for financial support. e-mail: fokin@tomo.nsc.ru P28 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND CHARACTERIZATION OF NEW BINUCLEAR (Sm2 AND Sm, Tb) LANTHANIDE PIVALATES I.G. Fominaa, Zh.V. Dobrokhotovaa, .B. Ilyukhina, G.G. Aleksandrova, V.O. Kazaka, . . Gehmana, N.N. Efimova, A.S. Bogomyakovb, A.A. Antoshkov c, Y.S. Zavorotnyc, V.I. Gerasimovac, V.M. Novotortseva and I.L. Eremenkoa a N. S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky Prosp, 31, Moscow, GSP-1, Russian Federation. b International Tomography Center of Siberian Branch of the Russian Academy of Sciences, 630090, Institutskaya Str. 3a, Novosibirsk, Russian Federation. c Skobeltsyn Research Institute of Nuclear Physics, M. V. Lomonosov Moscow State University, 119991, Leninskie Gory 1/2, Moscow, GSP-1, Russian Federation. The high-temperature solid-state desolvation under an inert atmosphere was studied for two new homobinuclear polymorphic complexes of the same composition (bath)2Sm2(piv)6·2EtOH (Piv = (CH3)3CCO2 , bath = 4,7-diphenyl-1,10-phenanthroline), which differ in the structural functions of the bridging carboxylate anions. This resulted in the synthesis of new non-solvated pivalate (bath)2Sm2(piv)6. New heterobinuclear complexes (bath)2SmTb(piv)6·2EtOH and (phen)2SmTb(piv)6 (phen = 1,10-phenanthroline) were synthesized by solution chemistry methods. The solid-state thermal decomposition of homobinuclear Sm pivalates with chelating N-donors, such as 2,2'-bipyridyl, phen [1], and bath, and heterobinuclear (Sm, Tb) pivalates with phen and bath ligands, was studied, the composition of the complexes in the gas phase was determined, and the magnetic and photoluminescent properties were analyzed. All complexes were characterized by X-ray diffraction. Luminescent metal-organic lanthanide compounds have attracted considerable interest as highly promising substances in the preparation of hybrid functional materials such as «molecule in the polymer matrix», including the method of supercritical fluid (SCF) impregnation. The physicochemical properties of binuclear (Sm2 and Sm, Tb) lanthanide pivalates obtained and known ( piv)6Tb2(piv)6, (bpy)2Tb2(piv)6, (phen)2Tb2(piv)6, and (bath)2Tb2(piv)6·2EtOH [2], after treatment in conditions SCF technology were studied. The experiments were carried out with the use of a SC- 2 (SC-carbon dioxide) as the SCF. [1] I.G. Fomina, M.A. Kiskin, A.G. Martynov, G.G. Aleksandrov, Zh.V. Dobrokhotova, Yu.G. Gorbunova, Yu.G. Shvedenkov, A.Yu. Tsivadze, V.M. Novotortsev and I.L. Eremenko, Russ. J. Inorg. Chem., 2004, 49, 1349-1359. [2] I.G. Fomina, Zh.V. Dobrokhotova, V.O. Kazak, G.G. Aleksandrov, K.A. Lysenko, L.N. Puntus, V.I. Gerasimova, A.S. Bogomyakov, V.M. Novotortsev and I.L. Eremenko, Eur. J. Inorg. Chem., 2012, 22, 35953610. Acknowledgements - This study was ﬁnancially supported by the Russian Foundation for Basic Research (Project Nos. 13-03-00470, 12-03-00627, 11-03-00556, 13-03-00408, 12-03-33062, and 12-03-31395), the Council on Grants at the President of the Russian Federation (Grants NSh-2357.2012.3 and NSh-1670.2012.3), the Ministry of Education and Science of the Russian Federation (SC-8437, SC-16.516.11.6137), the Target Programs for Basic Research of the Presidium of the Russian Academy of Sciences, and the Division of Chemistry and Materials Science of the Russian Academy of Sciences. e-mail: e-mail: a. fomina@igic.ras.ru, b. bus@tomo.nsc.ru, c. vis@srd.sinp.msu.ru. P29 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CIS-CONFIGURED MONONUCLEAR PALLADIUM(II) AND PLATINUM(II) COMPLEXES OF CHALCOGENO O-CARBORANES S. Glazuna, Z. Starikovaa, R. Takazovaa, A. Buyanovskayaa, P. Petrovskiia , M. Palb, V. Jainb, A. Wadawaleb, V. Bregadzea a A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119991 Moscow, RUSSIA. b Chemistry Division, Bhabha Atomic Research Center, Mumbai 400085, INDIA. The reactions of [MCl2(PP)] and [MCl2(PR3)2)] with 1-mercapto-2-phenyl-o-carborane, NaSeCarbPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCarbPh)2(PP)], [M(SeCarbPh)2(PP)] (M = Pd or Pt; PP = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3bis(diphenylphosphino)propane)) and [M(SCarbS)(PR3)2] (Carb = C2B10H10, 2PR3 = dppm, dppe, 2PEt3, 2PMe2Ph, 2PMePh2 or 2PPh3) [1]. These complexes have been characterized by elemental analysis and NMR (1H, 31P, 77Se and 195 Pt) spectroscopy. The 1J(Pt-P) values and 195Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCarbPh)2(dppm)], [Pt(SeCarbPh)2(dppm)], [Pt(SCarbS)(PMe2Ph)2] and [Pt(SCarbS)(PMePh2)2] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquire a distorted square planar configuration defined by two cis bound phosphine ligands and two chalogenolates donor atoms. The carborane rings are mutually anti in [Pt(SCarbPh)2(dppm)] and [Pt(SeCarbPh)2(dppm)]. [1] M.K.Pal, V.K.Jain, A.P.Wadawale, S.A.Glazun, Z.A.Starikova, V.I.Bregadze, J.Organomet.Chem., 2012, 696 (26), 4257-4263. Acknowledgements – Authors are grateful to the Department of Science and Technology (DST, India) and Russian Foundation for Basic Researches (project № 12-03-92696). e-mail: gsa@ineos.ac.ru P30 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia HEMIN PEROXIDASE ACTIVITY IN MICROHETEROGENEOUS MEDIA M. A. Gradova, A. V. Lobanov N. N. Semenov Institute of Chemical Physics of Russian Academy of Sciences, 119991, Kosygina str, 4, Moscow, RUSSIA. Hemin (Fe(III) protoporphyrin IX chloride) is often used in biomimetic catalysis as a model of some oxidoreductases and oxygen transport proteins containing heme as a prosthetic group. Catalytic activity of such model compounds is known to be influenced by the aggregation state of the porphyrin macrocycle, which strongly depends on the solvent nature, medium acidity and the presence of potential extraligands (especially -donors) in the reaction system. In this paper we report on hemin peroxidase activity in o-phenylenediamine (o-PDA) oxidation using hydrogen peroxide as an oxidant in surfactant and polyelectrolyte media. Peroxidase activity was determined by monitoring the increasing absorbance at 430 nm characteristic of the o-PDA oxidation product (2,3-diaminophenazine) in the course of the reaction. Hemin monomeric species predominant in anionic (sodium dodecyl sulfate, SDS) or neutral (Triton X-100) surfactants were found to possess a significant peroxidase activity due to both steric and electrostatic factors favouring the H2O2 molecule binding to the ferric central atom, leading to the formation of ferryl-type intermediates (Fe4+=O) - major oxidising agents. In alkaline medium with the predominant dimeric form of the catalyst such high-valence particles are responsible for rapid hemin oxidative destruction, and hence, the absence of peroxidase activity. In contrast, aggregated hemin species in acidic medium and hemin-surfactant or heminpolyelectrolyte ionic associates in cationic surfactant (CTAB, hexadecyltrimethylammonium bromide) micellar solutions or cationic polyelectrolytes (polydiallyldimethylammonium chloride, PDDA) exhibited extremely low peroxidase activity and oxidation rate, indicating the importance of extracoordination in the catalytic mechanism. Inorganic polyanions (SHMP sodium hexametaphosphate) were shown to significantly increase hemin peroxidase activity. The above findings correlate with the earlier obtained data on the rate of hemin oxidative destruction by hydrogen peroxide in various media, suggesting the novel mechanisms of catalytic activity regulation and switching between peroxidase and catalase activity for heminbased enzyme models. e-mail: m.a.gradova@gmail.com, a.v.lobanov@mail.ru P31 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia INVESTIGATION OF ORGANOMETALLIC COMPOUNDS BY JOINT USE OF MALDI-TOF MS AND CYCLIC VOLTAMMETRY Ivan D. Grishin, Ksenya S.Agafonova Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina prosp, 23/5, Nizhny Novgorod, RUSSIA. MALDI TOF MS is a powerful tool for analysis of labile and volatile compounds, such as organometallic species. A mechanism of molecular ion formation may be represented by a loss of an electron from HOMO orbital or transfer of electron from laser generated plum to LUMO. The molecular ions formed are either detected by mass analyser of undergo decomposition in case of their low stability. Their fragments are detected in the latter case. Cyclic voltammetry (CV) is a useful tool for exploration of electron transfer processes proceeding in liquid media. The stability of ions formed from organometallic compounds via oxidation or reduction is reflected in the reversibility of electrochemical processes. In this work the correlations between redox properties of organometallic compounds in CV studies and their MALDI MS spectra are done. Ferrocene and its derivatives such as (di)bromoferrocene and different mono- and bis(phosphino)ferrocenes undergo reversible one-electron oxidation in electrochemical cell in 1.2-dichloroethane. Such complexes give strong cation signal in positive mode mass-spectra. Paramagnetic ferracarboranes with diphosphine ligands undergo irreversible oxidation and irreversible reduction. No molecular ion is observed in their mass spectra. Fragmentation products are clearly seen indicating possible mechanism of decomposition. 17-electron ruthenium carborane complexes easily accept electron giving stable 18-electron species. It is reflected in reversible reduction to Ru(II) species in electrochemical cell and strong signals from molecular anions in mass spectra. 710 0.1 0.2 0.3 0.4 E, mV ver Ag/Ag+ 0.5 720 730 m/z So, it was found that compounds disposed to reversible oxidation give strong spectra in positive mode, while reversibly reducing compounds give spectra in negative mode. Acknowledgements - This work was supported Russian Ministry of Education and Science (“Federal target program of scientific and scientific-pedagogical personnel of innovation of Russia on 2009-2013”). e-mail: grishin_i@ichem.unn.ru P32 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia HIDROGEN BONDING AND OTHER SECONDARY INTERACTIONS IN IONIC LIQUIDS T. Grebneva and S. Katsyuba A. E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Centre of Russian Academy of Sciences, 420088, Arbuzova str, 8, Kazan, RUSSIA. Hydrogen bonds (H-bonds) have been suggested to be one of the molecular features which determine the properties of ionic liquids (ILs). Present study of the main features of H-bonds and other secondary interactions functioning in ILs is based on joint analysis of single-crystal X-ray data, quantum-chemical computations of isolated ion pairs and clusters of the ion pairs, and infrared spectra of several imidazolium- and phosphonium-based Ls. The general conclusion from this study and literature data is that H-bonds in isolated ion pairs are stronger than in the clusters and in bulk IL. In other words, H-bonding between counterions in IL is anticooperative. At the same time, cooperative strengthening of H-bonds formed between some self-associated cations is possible in bulk IL. These cooperativity/anticooperativity effects are especially pronounced in case of H-bonds formed with participation of strongly coordinating halide anions. The effects are not so dramatic for H-bonds formed by weakly coordinating perfluoroanions. In particular, OH...F bonds in IL are of approximately equal strength to analogous bonds formed in solutions of the same perfluoroanions in neutral molecular solvents of low polarity. Nevertheless, multiple secondary interactions functioning in bulk ILs, even being much weaker than interionic interactions within isolated ion pair, essentially influence the structure and vibrational spectra of ILs. Thus, such models as the isolated ion pairs or clusters of ion pairs cannot reproduce/predict the abovementioned characteristics of bulk ILs in detail. e-mail:.skatsyuba@yahoo.com P33 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia DENDRITIC IRON(III) COMPLEXES: SYNTHESIS AND PHASE BEHAVIOR M. Gruzdeva, U. Chervonovaa, A. Kolkera and N. Domrachevab a Institute of solution chemistry of the Russian Academy of Sciences, 153045, Akademicheskaya str, 1, Ivanovo, RUSSIA. b Zavoisky Kazan Physical-Technical Institute, Kazan Scientific Center, Russian Academy of Sciences, 420029, Sibirsky Tract 10/7, Kazan, RUSSIA One of the most important problem of modern chemistry is a creation of materials with controlled structure and target properties. Thereby coordination compounds containing Fe ions with azomethine ligands are of particular interest. One of their most important features is the ability of small modifications in the structure to significantly alter the key properties of the corresponding complexes. In this work a 29 iron(III)-containing mono- and biligand complexes based on azomethine were synthesized and characterized, which differ in structure of ligand and kind of counterion. A number of physicochemical methods were used to determine of the spatial environment of iron. Thus the formation of Schiff base (a strong absorption band at 1639 cm-1, which is characteristic of the (HC=N) bond) and the presence of the coordinated Fe3+ in the structure of the complexes (characteristic bands of the Fe(III) ion: Fe-N bond stretching vibrations, Fe-O bond stretching vibrations, M-anion bond vibrations in the far-infrared spectrum [1]) were established by FT-IR spectroscopy. The matrix assisted laser desorption/ionization (MALDIToF-MS) data indicate the existence of a series of stable ions characterizing the azomethine and iron(III) ions in its immediate environment. In addition IR spectra combined with data of mass-spectrometry and elemental analysis allow us judge about the symmetry of coordination of iron(III) ion with ligand and presence of one or another counter-ion and water molecules in complexes [2]. It was found that the structure of ligand effects on parameter of phase transition. Compounds based on azomethine formed by 2-aminopyridine exhibit mesomorphic properties in the absence of spin-crossover. Linear alkyl (dodecyl) on a periphery of ligand promotes ordering of complex structure. It is confirmed by reversible «crystal-crystal» phase transition in the cycle of heating and cooling and by high temperature of decomposition. In addition nature of counter-ion determines presence and behavior of phase transitions of branched chelate complexes of iron(III). Mesomorphic properties are characteristic for complexes with counterions, which can form associate by hydrogen bond: PF6-, BF4-, ClO4-. Spin state of iron ion was investigated to a number of complexes. For the first time branched biligand iron(III) complex based on azomethine 3,5-di(4-cyclohexanebenzoyloxi)benzoyl-4salicyliden-N’-ethyl-N-ethylenediamine with counter-ion Cl- was synthesized. This complex demonstrates spin transition (S=1/2 ↔ S=5/2) which induced and controlled by temperature [3]. [1] I.M. Cheremisina, Russ. J. Str. Chem., 1978, 19, 336. [2] M.S. Gruzdev, U.V. Chervonova, A.M. Kolker and N.E. Domracheva, Russ. J. Str. Chem., 2011, 52 (1), 8390. [3] M.S. Gruzdev, N.E. Domracheva, U.V. Chervonova, A.M. Kolker and A.S. Golubeva, J. Coord. Chem., 2012, 65 (10), 1812-1820. Acknowledgements – The work was carried out with the financial support of the grants of Russian Fundation for Basic Research № 12-03-31006-mol_a, № 11-03-01028 and Program of Presidium RAS № 24. e-mail: gms@isc-ras.ru P34 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPLEXATION OF TRINUCLEAR COPPER(I) AND SILVER(I) 3,5BIS(TRIFLUOROMETHYL)PYRAZOLATES WITH HALIDE LIGANDS Ekaterina Guseva, Aleksey Titov and Oleg Filippov. A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Russia, 119991, Moscow, V-334, Vavilova Str, 28, Moscow, Russia Macrocyclic pyrazolates of 11 group metals represent an important class of coordination compounds that can be used in areas such as supramolecular assemblies, hostguest chemistry and eximeric complexes with specific photophysical properties [1]. F3 C CF3 N N M F3 C M N N N M N CF3 CF3 F3 C Fe OC OC M = Ag, Cu CO Hal = Cl, Br Earlier we presented our studies of complex formation of macrocyclyc pyrazolates with boron hydrides [2] and the high affinity to hydride atom was shown. Halide and hydride ligands have somewhat similar chemical properties. Therefore we use organometallic compounds with halide ligands as guests for macrocycles. The complexation was investigated by means of IR spectroscopy (230-290K) in lowpolar solvents (CH2Cl2, hexane). Reversible complex formation of these macrocycles with halide containing bases was demonstrated on the example of iron π-allyl complexes ((RC3H4)Fe(CO)3X; R = H, Me, Ph, X = Cl, Br) for the first time. The sites of coordination, composition and thermodynamic parameters (ΔH°, ΔS°) were determined for all studied complexes in the solution. The two types of complexes (1:1 and 1:2 compositions, i.e. two molecule of base per one molecule of macrocycle) were determined in case of silver macrocycle at low temperature. The significant influence of the metal nature on complexation process was shown. The values of complex formation constants of π-allyl compounds with silver macrocycle greater by order of magnitude comparing to the copper analogue. [1] Omary, M. A.; Rawashdeh-Omary, M. A.; Gonser, M. W. A.; Elbjeirami, O.; Grimes, T.; Cundari, T. R.; Inorg. Chem. 2005, 44, 8200-8210. [2] V. N. Tsupreva, O. A. Filippov, A. A. Titov, A. I. Krylova, I. B. Sivaev, V. I. Bregadze, L. M. Epstein, E. S. Shubina, J. Organomet. Chem., 2009, 694, 1704–1707. Acknowledgements - This work was supported by Russian Foundation for Basic Research (project № 12-0300872) e-mail: katti_guseva@mail.ru P35 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NOVEL B-SUBSTITUTED CARBORANYLPROPYL(ORGANO)CHLOROSILANES. SYNTHESIS AND PROPERTIES B.A. Izmaylova, V.A. Vasneva and Shicheng Qib a A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences. 119991, VavilovaStr. 28, Moscow, Russia. b Beijing University of Chemical Technology. Beijing, China. The reaction of silicon alkylation of o-, m-, p-carboranes by chloropropyl-tri-, chloropropyl(methyl)di- and chloropropyl(dimethyl)clorosilane in the presence of catalysts of Friedel-Crafts reaction is studied. It is stated that specified organochlorosilanes silicopropilate are bounded the carborane cage by B-H bond. R' RCB10H10CR + ClCH2CH2CH2SiCl R' AlCl3 t RCB10H(10-n)CR R' CH2CH2CH2SiCl R' n , R= H, Ph; R’= Cl, Me; n= 1, 2. The catalysts of this reaction can be arranged in a line according to their activity:AlCl3 > AlBr3>BF3·Et2O>SnCl4>FeCl3 . Chloric iron was inactive. Apart from the ratio of the initial reagents, the mixture of mono- and disiliconepropyl derivatives of carborane nuclear is formed, easily separable by distillation, especially after methylation: RCB10H(10-n)CR RCB10H(10-n)CR CH3MgI CH2CH2CH2Si(CH3)3 CH2CH2CH2SiCl3 , n=1, 2. n n The structure of trimethylsilylpropyl radical and his connection with boron atom but not with carbon atom of the carborane was proved by IR-, PMR- and mass-spectra. In addition, some of the compounds obtained were introduced into the reaction with reactants, reacting with the active hydrogen atom (C-H) of the carborane cage. For this purpose we used the reaction with Grignards reagents, carried out in the Tserevitinov device, which allowed to determine quantitatively the existence of C-H bonds in compounds obtained by the volume of the released hydrocarbon The products of siliconpropilation and their methyl analogs are colourless liquids, distilling under vacuum. Chlorosylil derivatives are easily to hydrolized on air, alkoxysilylate by alcoholes, acylate by acetic acid, aminate by amines and ammonia, at the same time their tremethyl analogs are stable and can be stored on air for a long time without changing. e-mail: izmailov38@yandex.ru P36 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ORGANOANTIMONY AND ORGANOBISMUTH COMPOUNDS AS MONOMERS IN THE SYNTHESIS OF METAL CONTAINING POLYMERS O.S. Kalistratova, R.A. Verkhovykh, V.A. Verkhovykh, A.V. Gushchin University of Nizhni Novgorod, 23 Prospekt Gagarina, 603950, Nizhni Novgorod, Russia Triphenylantimony and triphenylbismuth derivatives can be used for the preparation of scintillation detectors in high energy physics. These compounds could increase the radiation stability of the scintillators. They also have some advantages over organometallic compounds of the lead and tin, which have previously been used for these purposes. They are less poisonous, more soluble in the monomers, more cheap. Furthermore C=C double bonds in the molecules, could provide the possibility to be copolymerized with the monomers and stabilize the polymers. The aim of the work was to obtain some triphenylantimony and triphenylbismuth derivatives with the carbonic acids, copolymerization of them with MMA and styrene to give metal containing polymers. Crotonic and cinnamic acids were used. The synthesis was carried out with the oxidation addition reaction of triphenylantimony or triphenylbismuth, acid and hydrogen peroxide or tert-butylhydroperoxide according to the reaction: Ph3 + 2R = COOH + H2O2 → Ph3 [O2CR]2 + 2H2O =Sb, Bi; R= CH3 = -, C6H5 = The obtained organometallic compounds were investigated by X-ray diffraction with the use of single-crystal diffractometer Oxford diffraction Geminis, 1H-NMR spectroscopy with Agilent DD2 400 and IR spectroscopy with Shimadzu IRPrestige-21. These compounds have trigonal bipyramidal structure with three phenyl groups in the base of the pyramid and two carboxylate groups in apical positions. Polymers containing different quantity of organometallic compounds were prepared and investigated with different methods. e-mail: Olga.Kalistratova@yandex.ru, roman-verkhovykh@yandex.ru, gushchin4@yandex.ru P37 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia RADICAL POLYMERIZATION OF METHYL METHACRYLATE IN THE PRESENCE SOME OF O-IMINOQUINONES A. Kaprininaa, L. Vaganovaa, A. Piskunovb and D. Grishina a Nizhny Novgorod State University 603950, Gagarin pr, 23/5, Nizhny Novgorod, RUSSIA. b G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences 603950, Tropinin str, 49, Nizhny Novgorod, RUSSIA. The sterically hindered o-quinones and o-iminoquinones are widely used as ligands in coordination and organometallic chemistry. The use of different quinones in macromolecular chemistry was studied in detail while the o-minoquinones are still unexplored. Comparison of the influence of compositions and structure some of o-quinones and oiminoquinones on the radical polymerization of methyl methacrylate (MMA) initiated by azobis(isobutyronitrile) (AIBN) at 70-90° was investigated. The following compounds were studied in this processes: But But O But O Q O O N Ar But N Ar imQ imPhenQ there Ar – 2,6-diisopropylphenil It was found that the role of these compounds in radical polymerization of MMA strictly depends on their structure. The benzoquinone Q under the reaction conditions acts as an inhibitor. Maximum conversion in ratio Q / AIBN = 1 / 1 at 70°C does not exceed 30%. The use of imPhenQ in equimolar ratio to the initiator has no effect either on the rate of the polymerization of MMA or the molecular weight characteristics polyMMA at 70-90°C. The introduction of imQ reduces the rate of polymerization of MMA in proportion to its concentration. Number average molecular weight of polyMMA increases linearly with conversion. The index of polydispersity of polymers is ~ 1.5-1.8 up to high degrees of monomer conversion. The postpolymerization of MMA and s nthesis of blo k- opolymers of MMA with styrene were performed on the basis of the macroiniti tors obtained with parti ipation of the studied imQ. These pro esses indic te possibility of reinitiating of polymerization and the dire ted fun tionalization of polymers. The obtained data evidence of simultaneous realization both the reversible acceptance of radical by imQ. These imQ stated above are capable of acting as regulators of chain growth for the polymerization of MMA. Acknowledgements - This work was supported by the Russian Foundation for Basis Research (project no. 11– 03–00674). e-mail: vaganova@ichem.unn.ru P38 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COORDINATION ABILITIES OF N,N-DISUBSTITUTED PHENANTHRENE-9,10-DIIMINES T. Kocherovaa, N. Druzhkova, I. Smolyaninovb, N. Berberovab and V. Cherkasova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b Astrakhan State Technical University, 414025, Tatisheva srt, 16, Astrakhan, RUSSIA. The series of novel N,N-disubstituted phenanthrene-9,10-diimines (PHDIIM) was synthesized by the condensation of 9,10-phenanthrenequinone with primary amines[1]. In the present research coordination properties of PHDIIM were studied. Compounds PHDIIM can act as neutral, radical-anionic and dianionic ligands in complexes depending upon the nature of the metal atom. The neutral complexes were synthesized in their reaction with the II group metal salts. The interaction of PHDIIM with excess of metallic potassium has not led to osemiquinonediimine complexes, that is in good agreement with the CVA data. The electrochemical reduction of PHDIIM is a two-electron process for nearly all compounds. In the reaction with rhodium carbonyl, radical-anionic complexes with chelate bonded metal atom were registrated by EPR spectroscopy in solution. The oxidative addition of PHDIIM to germanium dichloride leads to complexes of dianionic PHDIIM ligands. R' N + ZnI2 I R' I Zn N N + Rh4(CO)12 OC R N R R' Rh N CO R N + GeCl2 diox Cl R' N Cl Ge R N [1] V.K. Cherkasov, N.O. Druzhkov, T.N. Kocherova, A.S. Shavyrin, G.K. Fukin. Tetrahedron, 2012, 68, 14221426. Acknowledgements - This work was supported by Russian Foundation for Basic Research (13-0397103_r_povolzh’e_a, 12–03–31348_mol_a), Program for support of Leading Scientific Schools (NSh1113.2012.3) and Ministry of Education and Science of the Russian Federation (FTP “Scientific and ScientificPedagogical Personnel of Innovative Russia in 2009–2013” (Contract № 8465)). e-mail: tanya@iomc.ras.ru P39 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia DIFFERENT MECHANISMS OF RADICAL POLYMERIZATION OF METHYL METHACRYLATE IN THE PRESENCE OF COBALT COMPLEX WITH STERICALLY HINDERED O-IMINOBENZOQUINONE LIGANDS E. Kolyakinaa, Yu. Ovchinnikovaa, A. Poddel’skyb, and D. Grishina a Lobachevsky State University of Nizhny Novgorod, 603950, Gagarin Ave. 23/5, Nizhny Novgorod, RUSSIA b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. During the past fifteen years many techniques of controlled radical polymerizations (CRP) were developed for a wide range of monomers to attain well-defined polymers with controlled molecular weights, end functionalities, and narrow molecular weight distributions. The cobalt complexes find extensive application in the synthesis of macromolecules over the past decades. These complexes can mediate controlled polymerisation of various monomers via different mechanisms. Investigation of the mechanism of such processes is a major research focus of polymer science. In our work the different mechanisms of radical polymerization of methyl methacrylate (MMA) initiated by azobis(isobutyronitrile) (AIBN) in the presence of bis-[4,6-di-tert-butylN-(2,6-dimethylphenyl)- -iminobenzosemiquinonato]cobalt(II) (Co(ISQ-Me)2) were investigated (scheme). Processes were described by first-order of semilogarithmic plots of ln([M]0/[M]) versus time, linear growth of MW with conversion of monomer and synthesis of block copolymers. Additives of amines did not affect on the polymerization. P1 Co(ISQ-Me)2 I2 2I P1 kp + M + M kp P DTP +M kp P + P Co(ISQ-Me)2 Co(ISQ-Me)2 +M OMRP +M Co(ISQ-Me)2 + HM H Co(ISQ-Me)2 unstable kp +M CCTP (APH)Co(ISQ-Me) + P(-H) The analysis of polymers by MALDI-TOF, IR, UV and NMR spectroscopy showed that the probability of -hydrogen transfer (direction of CCTP) between the cobalt complex with sterically hindered iminobenzoquinone ligands and initiating or growing radicals minimized. The kinetic data of the MMA polymerization in the presence of various AIBN concentrations and a fixed concentration of Co(ISQ-Me)2 showed that the major mechanism of polymerization is DTP mechanism. Acknowledgements - This work was supported by Russian Foundation of Basic Research (pr. №11-03-00074). e-mail: kelena@ichem.unn.ru P40 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia STIMULATED RADIATION BY ORGANIC SEMICONDUCTORS T.N. Kopylovaa, A.V. Kukhtob, M.G. Kaplunovc, A.V. Yakimanskyd, E.N. Telminova, R.M. Gadirova, T.A. Solodovaa, K.M. Degtyarenkoa, E.N. Ponyavinaa a Siberian Physical Technical Institute of Tomsk State University, 634050, Novosobornaya sq., 1, Tomsk, RUSSIA b Belarusian State University, 220030, Independence av., 4, Minsk, BELARUS. The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432, Academician Semenov avenue 1, Chernogolovka, Moscow region, RUSSIA. d Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004, Bolshoy Pr, 31, St. Petersburg, RUSSIA. Investigation of stimulated radiation by organic semiconductors in thin films under photoexcitation is urgent from the viewpoint of creating organic semiconductor injection lasers that have not yet been created. It’s known that, organic semiconductors, which are used for OLED fabrication, are the most suitable types of materials for organic semiconductor lasers [1,2]. In the present work low- and high-molecular organic semiconductors DA-BuTAZ [3], metallo-organic complex with Zn(DFP-SAMQ)2 [4], biphenyls [5] and copolyfluorenes are investigated [6]. It was established, that upon excitation by radiation of the third harmonics of Nd3+:YAG lasing all compounds (except Zn complex) generate stimulated radiation in solutions and films. Spectra of spontaneous emission under photo- and electroexcitation are similar. Stimulated radiation for all researching compounds, except Zn complex, is established. It was shown that DA-BuTAZ generated stimulated radiation in TGF solutions ( gen = 450 nm) and films ( gen = 412 nm). The Zn(DFP-SAMQ)2 complex did not generate radiation even in solutions when the pump power density changed from 2.4 to 31.4 MW/cm2 and the radiation pulse duration exceeded twice the pump pulse duration. Theoretical and experimental investigation of the nature of the radiative state for Zn complex are continuing. Well radiating biphenyls in the simplest compositions under photoexcitation have both lowthreshold generation and electroluminescence that are of undoubted interest for investigation of deactivation of the excitation energy of various types in such structures and creation of organic injection lasers. Generation was observed in the region of polyfluorene emission gen = 440 nm with efficiency = 12% (W = 10 W/cm2) for copolymer 1 and efficiency = 5% (W = 7 MW/cm2) for copolymer 2. In films, copolymers generate in the region of polyfluorene emission, gen = 448 nm. Results demonstrate possibility of creation photoexcitated organic semiconductor lasers and it could be the first stage to the creation organic semiconductor injection lasers. [1] I.D.W. Samuel, G.A. Turnbull, Chemical Reviews, 2007, 107, 1272-1295. [2] S. Chenais, S. Forget, Polymer International, 2012, 61, 390-406. [3] I.K. Yakushchenko, M.G. Kaplunov, et.al., Physical Chemistry Chemical Physics, 1999, 1, 1783-1785 [4] . . , . . ., , 2010, 5 (7-8), 117-120. [5] . . , . . ., я я, 2013, . Acknowledgements – These researches are supported by grant of RF President (SS-512.2012.2) e-mail: kopylova@phys.tsu.ru P41 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia DYNAMIC PROCESSES IN CYCLOMETALLATED O-SEMIQUINONIC PALLADIUM COMPLEXES: EPR STUDY K.A. Kozhanova, M.P. Bubnov, V.K. Cherkasov and G.A. Abakumov a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. In present work we report on coordination of different phosphines to o-semiquinonic azophenyl palladium complexes and studying of different kinds of o-semiquinonic palladium complexes with pincer ligands. Reaction of azophenyl complexes 1a-c with PPh3 leads to reversible coordination of one or two phosphine molecules. Reaction with bidentate phosphines leads to formation of five-coordinated products. Bis-cyclometallated phosphine pincer complexes 2a-b demonstrates “fan” and “swing” oscillations whereas their phosphite analogs 3a-b exist as four-coordinated complexes without any coordination sphere dynamics. B ut O PR 2 O O B ut R2 P O Pd X Pd B ut O R 2P B ut B ut O X O O O PR 2 R 2P O Pd O P R2 O Acknowledgements – the work was supported by RFBR (grants 12-03-31087 and 13-03-01000) and Russian President (grant NSh-1113.2012.3). e-mail: kostik@iomc.ras.ru P42 B ut International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia O-QUINONES FUNCTIONALIZED WITH DIPHENYLMETHYL SUBSTITUENTS. LIGANDS CAPABLE TO CARRY MORE THEN ONE UNPAIRED ELECTRON. V. Kuropatova, V. Cherkasov a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Catechol has been alkylated with diphenylmethanol. The reaction proceeds at mild conditions and results in three main products. 3,5-, 4,5- and 3,4,5-substituted adducts have been isolated from the reaction mixture. OH + OH Ph2CHOH 1.H2SO4,  sol CHPh2 O CHPh2 O Ph2HC O 1 Ph2HC O Ph2HC + + O CHPh2 Ph2HC 2 O 3 Formation of essential amount of products 2 and 3 where bulky substituents are situated in the adjacent positions was surprising. Due to existence of methine proton in substituent these compounds potentially can be oxidized to give trityl-like stable radical. So, these quinones are regarded as potential multispin ligands. Chemical properties and coordination abilities of new quinones will be discussed. Acknowledgements - We are grateful to the Russian Foundation for Basic Research (grants N 13-03-01000, 13-03- 97103 r_povolzh’e_a), President of Russian Federation (grants NSh-1113.2012.3) for financial support of this work. This work was made according to FSP “Scientific and scientificpedagogical cadres of innovation Russia” for 2009e2013 years (Contract 8465 from 31.08.2012). e-mail: viach@iomc.ras.ru P43 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NMR INVESTIGATION OF LIGANDS EXCHANGE IN THE CALCIUM--DIKETONATE COMPLEX Yu.A. Kurskii, A.S. Shavyrin, and T.S. Pochekutova G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The motivation for investigation of properties of mixed ligands calcium-β-diketonate complexes with neutral poly-oxygen donor ligands is based on their use as high volatile compounds for preparation of calcium stable isotopes and a precursors for MOCVD. The complex [Ca2(adtfa)4](18-crown-6)](H2O)2(C2H5OH) (adtfa = 1,1,1-trifluoro-4-(1adamantyl)butanedionate-2,4), is the ion-paired solvated adduct, containing the cation [Ca(adtfa)(18-crown-6)(H2O)]+, the anion [Ca(adtfa)3(H2O)]− and solvated C2H5OH molecule, as showed by X-ray and NMR [1]. There are two forms of adtfa ligands with 3 : 1 stoichiometric ratio in the complex solution according to 1H and 19F NMR spectra at low temperature. The first one corresponds to the anion and the second – to the cation. Exchange of adtfa-ligands between the cation and the anion forms has been found by NMR. Rate constants of exchange at different temperatures have been determined by means of program Topspin 2.1 (DNMR). Rate of the reaction depends on ethanol concentration. Mechanism of the exchange reaction has been suggested and thermodynamic parameters have been determined. [Ca(adtfa)(18-crown-6)(H2O)]+ [Ca(adtfa)3(H2O)]− + C2H5OH   [Ca(adtfa)2(18-crown-6)] + [Ca(adtfa)2(H2O)2(C2H5OH)] Temperature dependence of the complex NMR 19F spectra in C6D5CD3 [1] T.S. Pochekutova, V.K. Khamylov, G.K. Fukin, Yu.A. Kurskii, B.I. Petrov, A.S. Shavyrin and A.V Arapova, Polyhedron, 2011, 30, 1945-1952. Acknowledgements – The work was supported by the Russian President’s grant supporting scientific schools (NSh-1113.2012.3). e-mail: kursk@iomc.ras.ru P44 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia BOND DISSOCIATION ENERGIES IN ORGANOMETALLIC COMPOUNDS: POLARIZABILITY EFFECT O.V. Kuznetsova, A.N. Egorochkin and N.M. Khamaletdinova G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Str., 603950 Nizhny Novgorod, RUSSIA Many studies of intramolecular interactions are used the correlation analysis of the so-called narrow series XnRC where RC is an indicator centre and Xn are substituents (Alk, Ph, F, …). For each of these series the centre RC remains fixed whereas the substituents Xn vary. The literature data on X substituents influence on the bond dissociation energies (BDE) have been analyzed for 10 narrow series of compounds XHgCl ([1], RC=HgCl), XHgBr([1], RC=HgBr), X2BCl ([1], RC=BCl), XC(O)SiH3 ([2], RC=SiC), XC(O)GeH3 ([2], RC=GeC), XC(O)SnH3 ([2], RC=SnC), XC(O)PbH3 ([2], RC=PbC), X3P=S ([1], RC=P=S), XBMn(5-C5H5)(CO)2 ([3], RC=MnB), and XC(O)Ir(CO)Cl2(PMe2Ph)2 ([4], RC=IrC). Up to now, the mechanism for the influence of X on BDE is not understood. It is unlikely that the BDE values of HgCl, HgBr, BCl, SiC, GeC, SnC, PbC, P=S, MnB, and IrC depend only on the inductive and resonance effects of substituents. Our approach is based on comparison of the two-parameter BDE = BDE0 + aI + bR(R+, R) (1) and four-parameter BDE = BDE0 + aI + bR(R+, R) + c + dEs’ (2) +  equation, where I is the universal inductive constant of substituents X; R, R , and R are the parameters characterizing the resonance effect of X in the presence of a small, large positive and large negative excess charge q, respectively, on the centre RC;  and Es’ are the polarizability and steric constants of substituents X. In all series in going from Eq. (1) to Eq. (2) the adjusted correlation coefficients increase, whereas standard errors of approximation decrease. This clearly demonstrated that BDE values depend on the inductive, resonance, polarizability, and steric effects of substituents. The homolytic dissociation of a bond (e.g. XHgClXHg + Cl) produces change in electronic structure of RC and thus gives rise to the excess charge q on RC. The polarizability effect consists in an electrostatic attraction between the q and the dipole moment induced by this charge in X substituents. [1] L.V.Gurvich et al., Rupture Energy of Chemical Bonds. Ionization Potentials and Electron Affinities, Nauka, Moscow, 1974 [2] H. Basch, T. Hoz, in: S. Patai (Ed.), The Chemistry of Organic Germanium, Tin, and Lead Compounds, vol. 1, Wiley, Chichester, 1995, p. 1. [3] K.K. Pandey et al., Eur. J. Inorg. Chem., 2011, 2045. [4] G. Yoneda, S.-M. Lin, L.-P. Wang, D.M. Blake, J. Am. Chem. Soc., 1981, 103, 5768. Acknowledgements - This work was supported by Russian Foundation for Basic Research (project 12-0331703) e-mail: olga@iomc.ras.ru P45 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURES AND LUMINESCENT PROPERTIES OF LANTHANIDE HEXAFLUOROISOPROPOXIDES D. Kuzyaev, E. Baranov, A. Cherkasov, M. Bochkarev G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The isopropoxides Ce(OPrF)3 and Gd(OPrF)3 (PrF = CH(CF3)2) were synthesized by the reactions of corresponding silylamide complexes Ln[(Me3Si)2N]3 with PrFOH in DME medium. The products were isolated as colorless crystals. X-ray analysis revealed that cerium complex Ce2(OPrF)6(DME)2 is a centrosymmetric dimer where two isopropoxide ligands are bridging and four ligands are terminal. The reaction of EuI2(THF)2 with two equivalents of KOPrF affords the europium(II) isopropoxide Eu(OPrF)2(THF)2. Efforts to synthesize the analogous ytterbium(II) complex were unsuccessful. X-ray analysis showed that the Yb isopropoxide is a mixed-valence trinuclear cluster Yb3(OPrF)7(THF)(Et2O) which contains one trivalent and two divalent ytterbium ions. Emission intensity, a. u. Among the obtained isopropoxides only europium complex has shown photoluminescence. Its emission spectrum contains a broad band in UV region picked at 330 nm which can be assigned to the rarely observed 4f65d1 → 4f7 transition of Eu(II). 500 400 300 200 100 0 300 330 nm 360 390 Acknowledgements - The work was supported by the Russian Foundation of Basic Research (Grants 13-0300097 and 12-03-31273 mol_a). e-mail: kuzyaev@iomc.ras.ru, mboch@iomc.ras.ru P46 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE THERMODYNAMIC CHARACTERISTICS OF PYRAZOLONATE RARE-EARTH COMPLEXES N.M. Lazarevb , .I. Petrova , G.A. Abakumova a b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. N.I. Lobachevsky Nizhny Novgorod State University, 603950, Gagarina av, 23, Nizhny Novgorod, RUSSIA Rare-earth pyrazolonates have the electroluminescent properties and have attracted growing attention as emissive materials for organic light-emmiting diodes (OLEDs). However, quantitative data on the volatility of these compounds are absent in the literature. The aim of this study was investigation of the thermochemical properties and vapor phase composition of pyrazolonate rare-earth complexes Ln(PMIP)3 (Ln = Y(I), Nd (II), Tb (III), Ho (IV), Er (V) Tm (VI), Lu (VII); PMIP-1−phenyl−3−methyl−4−isobutyryl −5−pyrazolonate). The complexes I-VII were synthesized according to the procedure described in [1]. These complexes are white amorphous powder. Rare-earth pyrazolonates were characterized by elemental analysis, IR spectroscopy and 1H NMR spectroscopy. The received compounds were purified by sublimation in vacuum for further experiments. The final compounds are crystalline substances and are dimeric [Ln(PMIP)3]2 (according to X-ray diffraction study). The thermal properties of new pyrazolonate rare-earth complexes were studied by differential scanning calorimetry (DSC), by the Knudsen’s effusion method (I, IV-VII) and by the Knudsen’s effusion method with mass spectrometrical determination of the composition of the gas phase on a standard MI-1201 mass spectrometr modified for thermodynamic studies and an APDM-1 monopolar mass analyzer adjusted to work with molecular beams over the mass range extended to 2500 amu (II and III). Melting and thermodynamic parameters of the melt were obtained using a differential scanning calorimeter DSC204F1 Phoenix (DSC) (Netzsch Gerätebau, Germany). The endothermic transition was detected for all complexes. This transition was associated with melting. Thermodynamic parameters of melting are calculated. The temperature dependence of the vapor pressure of these complexes was measured by the Knudsen’s effusion method. Vaporization temperature interval was chosen according to the DSC data (216-300 ◦ ). Thermodynamic parameters of sublimation are calculated: for complex I ∆sH=130.3±1.9 kJ/mol, for complex II ∆sH=205.9±2.7 kJ/mol, for comlexes III ∆sH=208.0±4.0 kJ/mol, for complex IV ∆sH=90.8±1.2 kJ/mol, for complex V ∆sH=83.9±1.4 kJ/mol, for comlex VI ∆sH=81.5±1.3 kJ/mol and for complex VII ∆sH=83.42±1.1 kJ/mol. It was found established that the dimeric complexes II and III are monomeric in the gas phase. This observation suggests that the complexes I, IV-VII behave similarly. In addition, according to mass spectrometry, the calculation of the vapor pressure was performed for the sublimation process into the monomeric vapor. [1] A.V. Safronova, L.N. Bochkarev, I.P. Malysheva, E.V. Baranov, Inorganica Chimica. Acta, 2012, 392, 454458. : nikolai-lazarev@mail.ru P47 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NONBENZENOID AROMATIC SYSTEMS WITH PARTICIPATION OF A METAL ATOM. VIBRATIONAL SPECTRA AND QUANTUM CHEMISTRY STUDY L.A. Leites, R.R. Aysin, S.S. Bukalov, A.N. Nesmeyanov Institute of Organoelement Compounds, Scientific and Technical Center on Raman spectroscopy, the Russian Academy of Sciences, Vavilova 28, Moscow 119991 Russia, Nonbenzenoid aromatic systems were a subject of Mark Vol’pin’s particular interest. Specifically, he paid much attention to creation chemistry of metallacyclopropenes, and the first example of such kind, namely, a complex Cp2Ti(PhC2Ph) not containing additional ligands was synthesized by him and co-workers in 1982, the three-membered metallacycle of this complex was considered as aromatic, its -electron delocalizes system involving two electrons of carbon atoms and the vacant orbital of the Cp2Ti species [1]. In this study, vibrational spectra of three types (I-III) of aromatic compounds, in which a metal atom participates in cyclic -electron delocalization, will be presented and discussed. These are two-electron metallacyclopropenes (I) as well as six-electron metallacyclocumelenes (II) [2] and Arduengo type N-heterocyclic unsaturated compounds (III): silylene [3] and germylene [4]. Aromaticity of compounds of these types will be estimated using different modern criteria, both experimental and theoretical (calculations of NICS and ISE). References: [1] (a) V.B. Shur, S.Z. Bernadyuk, V.V. Burlakov, M.E. Vol’pin, IInd All-Union Conf. Organomet. Chem., Abs. , Gor’ky 1982, p.178; (b) V.B. Shur, V.V. Burlakov, M.E. Vol’pin, J. Organomet. Chem. 1988, 347, 77. [2] R.R. Aysin, L.A. Leites, V.V. Burlakov, V.B. Shur, T. Beweries, U. Rosental, Eur. J. Inorg. Chem. 2012, 922. [3] L.A. Leites, S.S. Bukalov, M. Denk, R. West, J. Mol. Structure 2000, 550-551, 329. [4] L.A. Leites, S.S. Bukalov, A.V. Zabula, I.A. Garbuzova, D.F. Mozer, R. West, J. Am. Chem. Soc. 2004, 126, 4114. Acknowledgements The authors acknowledge partial financial support from the Russian Academy of Sciences in the framework of the program “Theoretical and experimental study of chemical bonding and mechanisms of chemical reactions and processes”. e-mail: buklei@ineos.ac.ru P48 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND STRUCTURAL STUDY OF COMPLEX COMPOUND OF COPPER WITH CYSTEAMINE D.Y. Leshoka, N.N. Golovnev and S.D. Kirik a Siberian Federal University, 660041, Svobodny pr, 79, Krasnoyarsk, RUSSIA. Reversible oxidation-reduction transformations between thiols (–SH) and disulphides (–SS–), play the important role in formation of ternary protein and enzyme structures. The reactions can be catalyzed by transition metal ions (Pd2+, Cu2+, Fe3+) [1,2]. In this respect the reactions of aminoacids with mentioned cations giving corresponding salts or complex compounds present certain interest for the protein biochemistry. In the present work the reaction between dihydrochloride cystamindium CystaH2Cl2 and CuCl2 following according to the equation: CystaH2Cl2 + CuCl2 → CystaH2[CuCl4] , (1) was studied and the product was structurally characterized using X-ray powder diffraction techniques and IR spectrum. CystaH2[CuCl4] was obtained from the acidic solution of the reactants with the molar ratio ysta : M2+ = 1 : 2. The 10 mol/l HCl was used as the solution to prevent a precipitation of CystaH2Cl2. The latter condition ensures the formation of the thermodynamically low stability anion [CuCl4]2− in the solution. According to thermal analysis, the decomposition of CystaH2[CuCl4] begins at 200 , giving CuO at 600 (weight loss 74.1%). To determine the structure of the complex IR spectrum of CystaH2[CuCl4] was compared to CystaH2Cl2. The minor displacement of the bands at 2900– 3200 cm-1 [(NH2)] and at 1560 –1600 cm-1 [ (C–N)] were indicated and explained as the lack of coordination of Cu2+ by nitrogen. This is confirmed by the presence of the bands at 1447– 1462 -1 and at 1578 – 1593 -1, referred to the symmetric bending vibrations of –NH3+ groups. The presence of CystaH22+ cation into CystaH2[CuCl4] was confirmed by X-ray crystal structure investigation, Figure 1: a b Figure 1 – Crystal structure and Rietveld plot of CystaH2[CuCl4] a – the structure of CystaH2[CuCl4] unit cell (a=7.18(3) Ǻ; b=7.50(3) Ǻ; c=12.01(1) Ǻ; β=101.2(0) o; V=635.1(4) Å3; P 21/a); b – diffraction pattern of CystaH2[CuCl4] The crystal structure of CystaH2[CuCl4] has a layered type (Fig. 1 a). The layers are built from cations CystaH22+ have a positive charge and alternate with layers consist of [CuCl4]2-. – NH3+ groups directed towards the corresponding halogen atoms from square planar [CuCl4]2-, whereby hydrogen bonds occur between them. [1] P. Allegra, E.Amodeo, S. Colombatto et al. //Amino Acids. 2002. V.22. P. 155. [2] A.V. Eryomin, V.G. Antonov, N.S. Panina et al. // Rus. Chem. J. 2009. V. 53. № 1. P. 135. P49 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia OBTAINING NANOPARTICLES TYPE OF CORE - SHELL, IN WHICH THE CORE -POLYMER AND THE SHELL - SILICON DIOXIDE. A. Lokteva, M. Baten’kin. G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Recently considerable interest is paid to the synthesis of porous nanoparticles based on silica. The intermediate phase for the synthesis of such particles is the production of core-shell type particles with followig removing of the core. The core is removed either thermally or by washing with solvent. The aim of our work is to develop methods for the preparation of nanoparticles in which a polymer is the core and silicon dioxide is the shell. Firstly, we prepared silica particles of 60-80 nm size by using the method of emulsifierfree emulsion polymerization of methyl metacrilate (MMA) and copolymerization of MMA with methacrylic acid (MAA), and vinylpyrrolidone and methacryloxyproryltrimethoxysilane (MPTMS). The particle size was determined by atomic force microscopy (ACM) on a microscope Solver P-47. The final particle size is given in the table. The resulting emulsion was carried out in an alkaline medium for hydrolysis of tetraethoxysilane (TEOS) for shell coating on the silica particles of polymethyl methacrylate and methyl methacrylate copolymers. The solution was dried to give films. Then again, the particle size was determined by the ACM. The average particle size increased, confirming availability of the silica coating on polymer nanoparticles. The data presented in the table. Table. size particles (nm) PMMA PMMA+TEOS MMA:MPTMS ММА:MPTMS + TEOS MMA:MAA MMA:MAA + TEOS ММА:N-VP ММА:N-VP+ TEOS 90 102 106 94 127 119 131 119 92 87 87 89 110 113 108 105 102 122 127 102 129 130 120 120 118 111 115 117 127 134 110 130 116 131 92 111 122 128 124 132 102 125 89 109 115 125 117 127 Acknowledgements – RFBR (grant 13-03-97026) e-mail: Lokteva@iomc.ras.ru P50 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF (CO)POLYMERS STYRENE IN THE PRESENCE OF SYSTEM ALKYLBORANE – QUINONE D.V. Ludina, Yu.L. Kuznetsova, S.D. Zaitsev a N.I. Lobachevsky Nizhny Novgorod State University Gagarin Prospekt 23/2, 603600 Nizhny Novgorod, e-mail: dymass@rambler.ru The polymerization of styrene at 80ºC initiated with AIBN has been studied in the presence of tri-n-buthylboron and a number of p-quinones: 2,3-dimethyl-benzoquinone, 1,4naphthoquinone, 2,5-ditertbuthyl-benzoquinone, duroquinone. The polymerization proceeds in a controlled manner according to the mechanism of Stable Free Radical Polymerization (SFRP): Formed adduct (I) is able to reinitiate (co)polymerization: (I) The most active macroinitiator has been obtained in the presence 2,3-dimethyl-benzoquinone and 1,4-naphthoquinone. The prepared macroinitiators were studied in the blockcopolymerization with methyl methacrylate and N-vinylpyrrolidone. This process passes with high rate, average number molecular mass (Mn) of block-copolymers (1.09 – 2.03)×106, Mw/Mn = 1.29 – 1.49. The content of styrene in the products ranges between 9 – 11% at deep conversion. The binary copolymerization of styrene with vinyl acetate proceeds in a controlled manner in the presence of tri-n-buthylboron and 2,3-dimethyl-benzoquinone too. A gradient copolymer with low compositional heterogeneity was synthesized by this type of copolymerization. P51 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia BIS(IMINO)ACENAPHTHENE (DPP-BIAN)-SUPPORTED N-HETEROCYCLIC SILILENE A.N. Lukoyanova, N.M. Khvoinova and I.L. Fedushkin a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. N-heterocyclic silelenes are not particularly amenable to ligand tuning by changing the steric and electronic characteristics of the substituents. Ligands of the bis(imino)acenaphthene (BIAN) class seemed like promising candidates for fusion to N-heterocyclic silelenes (NHSs), not only because of their structural rigidity, but also on account of their redox behavior. The annulation proposed herein would result in an Arduengo-type NHS.1 The bis(imino)acenaphthene-supported N-heterocyclic sililene (dpp-BIAN)Si has been prepared by reaction of dpp-BIAN with SiCl4 and potassium graphite. Pri i Pri Pr N i N + 4 KC8 + SiCl4 Si N Pri Pr N i Pri Pr i Pr Interaction of metal complexes with reduced dpp-BIAN-4 forms like (dpp-BIAN)Na4 with SiCl4 and SiBr4 gives a lot of by-products. However reactions of (dpp-BIAN)Na2 and (dppBIAN)Mg with SiCl4 produce (dpp-BIAN)SiCl2 with high yields. [1] A. J. Arduengo, III, R. L. Harlow and M. Kline, J. Am. Chem. Soc., 1991, 113, 361. Acknowledgements - This work was supported by the Russian Ministry of Education and Science (14.740.11.0613) and by the Russian Foundation for Basic Research (12-03-33080). e-mail: anton@iomc.ras.ru P52 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CONDUCTIVITY OF CRYSTALS AND VACUUM DEPOSITED FILMS OF COBALT O-SEMIQUINONATO COMPLEXES A. Luk’yanova, V. Cherkasovb, M. Bubnovb, N. Skorodumovab, V. Travkina, G. Pakhomova, S.Koroleva and P. Yunina a Institute for Physics of Microstructures of Russian Academy of Sciences, 603950, GSP-105, Nizhny Novgorod, RUSSIA. b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Molecular crystals of organic substances and organometallic complexes attract a great attention due to their unique properties such as conductivity and responsibility to light and heating. Some of these properties open possibilities for design of different sensors and active elements for molecular electronics. In this work the temperature dependence of conductivity of crystals and thing films of cobalt o-semiquinonato complexes ((2,2’-bpy)Co(3,6-DBSQ)2 (I) and (1,10-phen)Co(3,6-DBSQ)2 (II)) have been investigated. Crystals of a size until 2 mm length were grown from ether solutions. Electric contacts were created by thermal vacuum deposition of gold or by gluing of copper wares by a silver conductive paste. Thin films with thickness of 100-300 nm were produced by thermal vacuum deposition. They have polycrystalline or amorphous structures depending on the process conditions. For example, polycrystalline film can be made from amorphous one by annealing. Bottom electric contacts in sandwich structures were ITO on glass surface. Top electric contacts were produced by thermal vacuum deposition of gold. It was shown that 1) thermal response in conductivity of all samples is reversible; 2) conductivity of crystals exhibits an anisotropy; 3) amorphous, polycrystalline and crystal samples have different dependences of conductivity on temperature. Maximal change of conductivity of crystals (until 10 % per K) was observed in temperature ranges 270-310 K for complex I and 140-230 K for complex II. These temperature regions match with temperature intervals of phase transitions which were observed earlier [1, 2]. Values of conductivity at temperatures exceeding the transition intervals approximate to “zero” (noise level). Total value of changes exceed 100 times. It makes these complexes very promising to be applied for designing of uncooled bolometers. [1] G. Abakumov et all, Dokl. Akad. nauk, 1993, v.328, №3, 332-335. [2] M. Bubnov et all, Rus. Chem. Bul., Chemistry, 2011, №3, 440-446. Acknowledgements: We are grateful to the RFBR (grants №№ 13-03-97082, 13-03-97070, 13-03-12444), Russian President Grant supporting Scientific Schools (NSh-1113.2012.3) and Fundamental Research Programm of Presidium of RAS (№ 18) for financial support. e-mail: luk@ipmras.ru P53 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE BIS-O-SEMIQUINOLATE COMPLEXES OF II GROUP METALS: THE CORRELATION BETWEEN STRUCTURE AND MAGNETIC PROPERTIES A.V. Maleeva, A.V. Piskunov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The present work is directed on the obtaining new metal complexes of redox-active ligands with the controlled geometry and magnetic properties. The application of non-transition metals will allow to establish the general regularities of the magnetic interaction between the radical ligands excluding the influence of the paramagnetic metal. The obtained data array will help us to reveal the patterns of control on the intramolecular electronic and magnetic interactions metal-ligand and ligand-ligand in order to identify approaches to building of molecular magnetic and molecular devices based on the organometallic and coordination compounds with redox-active ligands. The series of zinc (or magnesium) bis-o-semiquinolate based on 3,6-di-tert-butyl-obenzoqunone or 5,8-di-tert-butyl-2,3-dihydro-1,4-ethanoquinoxaline-6,7-dion with different N,N-ligands was synthesized: t-Bu t-Bu t-Bu O R + R L L O R O R O R M M R O O L L t-Bu t-Bu t-Bu L L M = Zn, Mg , = N N , N N N Me phen Dipy , R-R = H,H; N N Me Me-phen Me N t-Bu N CH , HC N t-BuDAD t-Bu Me N Me CH HC KsDAD N Me All complexes were characterized using IR-, EPR-spectroscopy and elemental analysis. For some complexes measurements of magnetic susceptibility and X-ray structures were carried out. Two zinc complexes with phen and Me-phen ligands are monomers. The central metal atom in these complexes has an octahedral environment. In contrast to the latter, zinc complexes with diazabutadiene ligand are dimers. In this case -2-bound diazabutadiene has trans-configuration and environment of zinc is a distorted tetrahedral pyramid. Acknowledgements - We are grateful to the Russian President Grants (NSh-1113.2012.3) for financial support of this work. e-mail: arina@iomc.ras.ru P54 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REACTION OF DIPYRRIN BF2(I) COMPLEX FORMATION: EXPERIMENTAL STUDY AND THEORETICAL CALCULATIONS Yu. Marfina, S. Usoltseva, E. Rumyantseva and E. Antinab a Ivanovo State University of Chemistry and Technology, Department of Inorganic Chemistry, 153000, Sheremetevsky str, 7, Ivanovo, RUSSIA b G. A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 153045, Akademicheskaya str, 1, Ivanovo, RUSSIA. Bodipy-based dyes (Boron Dipyrrin complexes) and their various derivatives are being considered as promising components of functional materials for a variety of practical applications due to their unique spectral and photophysical properties, namely a high extinction coefficient, high fluorescence and the sensitivity of the spectral and photophysical properties to small changes in pH as well as to the polarity of the medium and low concentrations of metal ions. Despite the considerable interest in the Bodipy chemistry, the complexation mechanism of these compounds is not fully understood. Earlier in our research group the formation of a stable intermediate (donor-acceptor complex or DAC) in the synthesis of Bodipy starting from alkylated dipyrrin was indicated for the first time by the analysis of the reaction mixture followed by chromatographic separation [1]. This study is aimed to a more detailed study of the formation of donor-acceptor complex and its transition to Bodipy. Spectral analysis (IR, H1 NMR and Electron Absorption spectroscopy) and computer modeling was used to study the reaction, to determine the energy and geometric characteristics of the starting compound, intermediate and products of the reaction, as well as for calculation of reaction PES profile. It was shown that the formation of the DAC with BF3, further stabilized by hydrogen bonds N-H···F-B, is the first stage of Bodipy formation. The stability constants (in benzene and dimethylformamide), structural and energy parameters (gas phase) of DAC were defined. Analysis of a two-step reaction route of Bodipy synthesis indicates a high activation barrier for the transition of intermediate to Bodipy. To create more favorable conditions elimination of HF in the last step of the reaction was recommended to use electron-donating reagents. The main factor determining the difference in the enthalpy of formation of the donor-acceptor complexes of dipyrrins with halides of B (III), Al (III), Ga (III), In (III), As (III) and Sb (III), is the mutual cancellation of the energies of formation donor-acceptor bonds N → Element(III) and N-H···Hal–. A significant contribution to the stabilization of complexes with p-elements fluorides is making by the hydrogen bonds N-H···F–. It was shown that the second stage – the closure of the coordination cycle is kinetically controlled. The kinetic parameters and activation energy for the reaction processes were determined, reaction intensification routes have been proposed. [1] E. Rumyantsev, A. Desoki, Yu. Marfin and E. Antina, Russian Journal of General Chemistry, 2010, 80, 1871-1875. Acknowledgements - the work was supported by program of Federal Target Program “Scientific and scientificpedagogical personnel of innovative Russia” for 2009–2013 (State Contract no. 14.740.11.0617 and 14.132.21.1448). e-mail: marfin@isuct.ru, ymarfin@gmail.com P55 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SOLVENT EFFECTS ON DIPYRRIN COMPLEXES SPECTRAL AND PHOTOPHYSICAL PROPERTIES Yu. Marfina, D. Merkusheva, G. Levshanova, E. Rumyantseva and E. Antinab a Ivanovo State University of Chemistry and Technology, Department of Inorganic Chemistry, 153000, Sheremetevsky str, 7, Ivanovo, RUSSIA b G. A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 153045, Akademicheskaya str, 1, Ivanovo, RUSSIA. Chemistry of dipyrrins and their complexes got under extensive development nowadays. Possibilities of using the dipyrrin compounds are determined by dipyrrin intense chromophoric and fluorescent properties. This fact could be explained by the presence in their structure the labile π-electron system which is sensitive to changes in the external environment and the complexes structure. These compounds could be used to create analytical sensors for determination of ions, molecules, characteristics of the environment and as markers for biologically active molecules. Variation of the types of intermolecular interactions in dipyrrin complexes solutions is one of the main ways of controlling the spectral and photophysical properties of the considered chromophores and thus their valuable characteristics. Taking that into account the study of dipyrrin complexes solvatochromic characteristics (i.e. environmental effects on the spectral and photophysical properties) is the topic of great interest. The influence of solvents of different groups (electron and proton donor, polar and non-polar, viscous and fluid) on the characteristics of the absorption and fluorescence of dipyrrin complexes with p-and d-elements were examined as a part of the work. In the study of the viscosity influence binary solvent mixtures of ethanol and ethylene glycol, as well as the variation of the solution temperature was used to change the dynamic viscosity of the system. The solvent effects were examined using one-parameter and poly-parameter correlations of various solvent characteristics. It is shown that the complexes exhibit negative solvatochromic effect, i.e. hypsochromic magnitude of displacements in the absorption and fluorescence spectra increases with increasing solvent polarity. It was found that specific solvent-solute interactions make considerable contribution to the spectral properties of the compounds. The dipyrrin complexes containing phenyl moiety in the molecular structure of the ligand exhibit the molecular rotor properties. The fluorescence intensity is increases with increasing the dynamic viscosity of the solvent for such compounds. The changes in viscosity by varying the composition of the solvent lead to extreme dependence in the fluorescence spectra due to specific solvation. At the same time, changes the dynamic viscosity due to changes in temperature leads to a linear change in the emission spectra and complexes quantum yield. The authors separated the contributions of temperature and viscosity on the spectral characteristics of the complexes. The obtained results provide additional insight into the influence of solvation factors on the spectral and photophysical properties of the dipyrrin complexes and form the single strategy of selection and application of the compounds of this class. Acknowledgements - the work was supported by program of Federal Target Program “Scientific and scientificpedagogical personnel of innovative Russia” for 2009–2013 (State Contract no. 14.740.11.0617 and 14.132.21.1448). e-mail: marfin@isuct.ru, ymarfin@gmail.com P56 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia MIXED LIGAND COMPLEXES OF REE CARBOXYLATES AND BETA-DIKETONATES WITH N,O- AND N,N-DONOR LIGANDS: FEATURES OF SYNTHESIS, STRUCTURES AND THERMAL STABILITY I.A. Martynova, D.M. Tsymbarenko and N.P. Kuzmina a Lomonosov Moscow State University, 119991, Leninskie gory, 1-3, Moscow, RUSSIA. The mixed ligand complexes (MLCs) of rare earth elements (REE) carboxylates and beta-diketonates with organic neutral ligands are well studied and widely used classes of coordination compounds with different functional properties. So, in Chemical Solution Deposition (CSD) method, active developing recently for deposition REE-containing thin films, the combination of REE carboxylates and/or beta-diketonates with such amines (Q) as monoethanolamine (NH2CH2CH2OH, MEA) or diethylenetriamine (NH(CH2CH2NH2)2, DETA) are recognized as effective precursors. These amines exhibit dual nature. On the one hand, they are weak bases and promote to hydrolysis of REE coordination compounds. On the other hand, both MEA and DETA are N,O- and N,N-donor ligands which can take part in formation of mixed ligand complexes with unique structure and properties. The chemical behaviour of these amines in respect to REE carboxylates and beta-diketonates depends on thermodynamic stability of REE compounds, synthesis procedure. The interaction features of REE carboxylates, Ln(Carb)3, and beta-diketonates, Ln(βdik)3, (Ln = La, Eu, Ce, Lu, Y) with MEA and DETA were studied by examples of four carboxylic acids: acetic (HAcet), propionic (HProp), pivalic (HPiv), trifluoroacetic (HTfa) and two beta-diketones - acetylacetone (Hacac) and dipivaloylmethane (2,2,6,6-tetramethyl heptanedione, Hthd). Here we present interesting examples of new REE MLCs, which formed as polynyclear hydroxocompounds or as mononuclear compounds with ancillary amine ligands. For syntheses of MLCs we suggested new synthetic approach - interaction of hydrated REE nitrates with ion pairs of general formula [QHxx+][Carb-]x (Q = MEA, DETA) or Schiff bases (from Hacac or Hthd and Q). The formation of these ion pairs and Schiff bases was confirmed in non-aqueous solutions by potentiometry, electrospray ionization mass spectrometry (ESI MS), 1H NMR analyses and in solid state by X-ray crystal analysis. The hydrolysis process is suppressed completely only in syntheses with [QHxx+][Piv-]x ion pairs and Schiff bases. The MLCs of general formula [Ln(L)3-x(NO3)x(Q)y)] (HL = HPiv, Hacac, Hthd) were obtained and crystal structures of [Ce(Piv)5(MEAH+)][MEAH+] (I) [Ln(Piv)2(DETA)2](NO3) Ln = Lu(II), Y(III)) and [Ce6(O)8(Piv)8(DETA)4] (IV) were determined. Complexes I-III are the rare examples of mononuclear REE carboxylates with bulk ancillary ligands. In complexes I-IV carboxylate ligands did not show bridging function. Complex I is the first example of compound where MEA acts as O-coordinated and NH3+protonated ligand simultaneously. The results obtained are of interest to REE coordination chemistry as well as to chemistry of CSD precursors, as properties of these precursors strongly depend on MLCs composition. This work was supported by RFBR (project No 11-03-01208). e-mail: irinamartynova87@gmail.com P57 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia FIRST USE OF THE PHOSPHORYLATED CAGE METAL COMPLEXES AS CHELATING LIGANDS: PALLADACYCLES FORMED BY IRON(II) CLATHROCHELATES WITH P,N-DONOR RIBBED SUBSTITUENTS AND THEIR CATALYTIC ACTIVITY IN SUZUKI CROSS-COUPLING REACTIONS E.V. Matveeva, O.I. Artyushin, A.V. Vologzhanina, S.E.Lubimov and Y.Z. Voloshin A. N. Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, 119991, Vavilova st, 28, Moscow, RUSSIA. Recently reported phosphorylated iron(II) clathrochelates [1] with donor groups are promising ligands for the design of polytopic and multifunctional molecular and supramolecular systems, in particular, redox-switchable homogeneous catalysts. New phosphorylates iron(II) clathrochelates with P,N-donor functionalizing ribbed substituents were obtained by nucleophilic substitution of the macrobicyclic precursor 1 with primary (2 and 3) and secondary (4) amines as nucleophiles (Scheme). O N N O F S B O O P N N CH3NHCH2CH2SCH3 M2+ (C2H5)3N N N NCH2CH2SCH3 O O CH3 B F 4, 70% O N N O F B O O N N M2+ N N O O B F S O N P H2N(CH2)n Cl N (C2H5)3N N O F S B O O P N N M2+ N N N N(CH2)n O O H B n=1 (2) 89% F n=2 (3) 90% 1 Pd(C6H5CN)2Cl2 Pd(C6H5CN)2Cl2 O N N O (C2H5)3N F B O O P N N S Cl Cl M2+ Pd2+ N N N O O SCH3 B H3C CH2CH2 F O N F B O O N N P 2+ M N O 7 N N O O B F N S Cl Pd2+ N (CH2)n n=1 (5) 90% n=2 (6) 92% Scheme Their reactions with Pd(C6H5CN)2Cl2 afforded the corresponding clathrochelate-containing palladacycles: one formed by ternary donor amino group (7) is unstable and was spectrally detected only in a solution, but those with deprotonated secondary amino groups were isolated and characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-vis, 57 Fe Mössbauer, 1H, 11B, 19F, 13C{1H} and 31P NMR spectroscopies, and by X-ray crystallography. These clathrochelate-containing palladacycles showed high catalytic activity in model Suzuki cross-coupling reactions. [1] I.L. Odinets, O.I. Artyushin, E.V. Matveeva, A.V. Vologzhanina and Y.Z. Voloshin, Phosphorus, Sulfur, Silicon and Related Elements, 2013, 188, 159-161. Acknowledgements. This work was supported by RFBR (grant 12-03-31581). e-mail: matveeva@gmail.com, voloshin@ineos.ac.ru P58 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia PROCESS FOR PREPARING NONSOLVATED ALUMINUM HYDRIDE IN DIBUTYL ETHER P. Menkovaa, P. Storozhenko and O. Shutova a P.S. Menkova State Research Institute of Chemical Technology of Organoelement Compounds, 105118, Enthusiasts highway, 38, Moscow, RUSSIAN. The existing technology of obtaining nonsolvated aluminum hydride is based on Schlesinger, which consists of interaction lithium aluminum hydride and aluminum chloride in the mixture of diethyl ether and toluene. One of the main weaknesses of this technology is using diethyl ether, as this solvent is a precursor and a low-boiling one. In technological terms, one of the weaknesses is to use of large amounts of solvents mixture, which complicates their regeneration. In this regard, there is need to replace the system of solvents on the individual solvent. As solvent was selected dibutyl ether because this solvent is high boiling, not a precursor. In addition the use of this individual solvent increases the effective concentration of aluminum hydride. In connection with high demands to the quality of raw materials used in the synthesis of hydride compounds, was developed a method of deep cleaning of dibutyl ether from impurities such as peroxides, t-BuOH, BuOH and water [1]. It was studied the influence of impurities formed during decomposition of dibutyl ether, on the processes of synthesis and crystallization of aluminum hydride. Were investigated the following parameters of the processes of synthesis and crystallization of aluminum hydride: change the effective concentration of aluminum hydride, excess of lithium aluminum hydride, temperature regimes of synthesis and crystallization of aluminum hydride, type of seed(). Based on these studies were selected conditions of synthesis and crystallization of aluminum hydride in dibutyl ether. In result on the research was obtained β - and a-modification of aluminum hydride in dibutyl ether medium. [1] P.S. Menkova, P.A. Storozhenko., O.G. Shutova, Chemical industry. 2012, 89(6), 267 - 272. . e-mail: menkova-polina@yandex.ru, bigpastor@mail.ru, shutova@eos.su. P59 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia MOLECULAR CONDUCTORS: CHAINS OF THE COMPOUNDS CONTAINING ELEMENT-ELEMENT (Ge, Si, Sn) BONDS a a a a a a E.P. Moshkin , K.V. Zaitsev , V.A. Tafeenko , A.V. Churakov , S.S. Karlov and G.S. Zaitseva a b Chemistry Department of M.V. Lomonosov Moscow State University, 119991, Leninskie gory, 1, 3, Moscow, RUSSIA N.S. Kurnakov General and Inorganic Chemistry Institute of Russian Academy of Sciences, 119991, Leninskii avenue, Moscow, RUSSIA. At present time, the so-called "molecular wires" are of special scientific interest and is of practical importance in molecular electronics and nanotechnology. Usually the main objects of study in this area are organic compounds containing a system of conjugated carbon-carbon bonds. However, recently molecules containing non-carbon chain atoms, such as Ge, Si, Sn (E), attract significant attention. Electrons of the single E-E bond are delocalized over the entire chain of atoms of elements (σ-conjugation). Thus, the existence of σ-delocalization in oligogermanes and related compounds leads to the appearance of properties which are characteristic for unsaturated hydrocarbons (conductivity, thermochromism, non-linear optical properties etc.). The changes in the structure of compounds effect on these properties. The most important are: 1) the number of atoms of the elements in the chain [1]; 2) introducing additional donation to one of the atoms (Ge, Si or Sn) in chain [2]; 3) the electronic properties of substituents (electron withdrawing or electron donating groups) at atoms of Ge (Si, Sn) in the chain [3]. The report presents the results on the synthesis of oligogermanes and related compounds containing germanium-silicon and germanium-tin bonds. The structures of all compounds were investigated by multinuclear NMR spectroscopy, UV spectroscopy, and in some cases by X-ray analysis. References: [1] C.S. Weinert, Dalton Trans. 2009, 1691. [2] K.V. Zaitsev, A.A. Kapranov, Y.F. Oprunenko, A.V. Churakov, J.A.K. Howard, B.N. Tarasevich, S.S. Karlov, G.S. Zaitseva, J. Organomet. Chem. 2012, 700, 207. [3] M.N. Bochkarev, N.S. Vyazankin, L.N. Bochkarev, G.A. Razuvaev, J. Organomet. Chem. 1976, 110, 149. Acknowledgements - This work is supported by the RFBR (project 12-03-31153_mol-a). e-mail: zaitsev@org.chem.msu.ru P60 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia DIVERSITY OF GOLD (I) COMPLEXES OF 1,5-DIAZA-3,7DIPHOSPHACYCLOOCTANES. E.I. Musina,a I.D. Strelnik, Yu.S. Spiridonova, A.V. Shamsieva, T.I. Fesenko, A.S. Balueva, A.A. Karasik, O.G. Sinyashin a A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center of Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan (RUSSIA) Gold (I) complexes of diphosphines attract an attention due to their biological activity (in particular as anticancer drugs) [1] and the ability to form systems with metal-metal bonds, which have useful physical properties (e.g. luminescence, fluorescence etc.) [2,3]. It has been shown [4a,b], that cyclic aminomethylphosphines coordinate transition metals of 10 group to give P,P-chelate complexes, but complexes with metals 11 group were poorly investigated. Ligands were prepared by the Mannich condensation in system primary phosphine– formaldehyde - primary amine [4]. Reaction of 1 with one equiv. of AuCl led to mononuclear complex 5 whereas 2-4 with less bulky substituents on phosphorus formed unusual binuclear charged macrocyclic structures 6-8. Complex 6 demonstrated a noticeable water-solubility due to the presence of additional pyridyl groups. Reaction of 2-4 with two equiv. of AuCl gave binuclear compounds 9-11. The addition of 2 or 4 to gold (I) chloride in molar ratio 2 : 3 led to the formation of trinuclear complexes 12 and 13, which were isolated in good yield. X-ray data of compounds 6, 11 and 13 showed that in all cases gold (I) has a typical linear configuration but heterocycle has “crown” conformation for 11 and 13, and slightly twisted “chair – boat” conformation for 6. [1] P.Barnard, S. Berners-Price, Coord. Chem. Rev., 2007, 251, 1889–1902. [2] I. Koshevoy, C. Lin, A. Karttunen, M. Haukka et al., Chem. Commun., 2011, 47, 5533–5535 [3] V. Pawlowski, H. Kunkely, A. Voglert, Inorg. Chim. Acta, 2004, 357, 1309-1312 [4] a) S.N. Ignatieva, A. Balueva, A. Karasik et al., Inorg. Chem., 2010, 49, 5407-5412; b) A. Karasik, R. Naumov, A. Balueva et al., Heteroatom. Chem., 2006, 17,499-513; c) G.Maerkl, G.Yu. Jin, C.Schoerner, Tetrahedron Lett., 1980, 21, 1409-1412. Acknowledgements This work was supported by RFBR (No.13-03-00563- , 12-03-97083-r_povolzhie_a), President’s of RF Grant for the support of leading scientific schools (No.NSh-6667.2012.3). e-mail: elli@iopc.ru P61 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND STRUCTURE OF PYRAZOLATE- AND PYRAZOLATECARBOXYLATES COMPLEXES OF 3D-TRANSITION METAL ANALOGUES 1,10 PHENANTHROLINE OR 2, 2'-DIPYRIDINE I.V.Nefedova , M.A.Uvarova, A.A.Ageshina, M.V.Andreev, M.A.Golubnichya, S.E.Nefedov N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky pr,31, Moscow, RUSSIA Using transition metal carboxylates as deprotonating agents to coordinated pyrazole molecules leads to the formation bi-, homo trinuclear - heterometallic complexes. It was found that interaction PhenPd(OOCMe)2 (1) with Cu(Hdmpz)2(OOCR)2 or M2(µdmpz)2(Hdmpz)2(OOCR)2 (M = Zn, Co, R = But, Me, Ph, Hdmpz -3,5-dimethylpyrazole) formed complexes with metallocore Pd-Cu, Pd-Co, Pd-Zn2. These complexes contain a fragment PhenPd (dmpz 2 which is an analogue of the chelating Phen or dipy, which was donates 4 electrons. Despite the fact that these fragments find in a free state has not been possible, their analogue, - complex PhenPd[(CF3)2pz]2 was obtained by reacting 1 with 3,5trifluoromethylpyrazole (2). Similar reactions PhenM(OOCR)2 (M = Zn, Cu, Co) leads depending on the nature of the transition metal, R, pyrazoles and reaction conditions to form bis-pyrazolate PhenM(pz)2 or pyrazolate -carboxylates PhenM(pz)(OOCR) complexes. Thermolysis of the acetates of zinc, copper and cobalt in the presence Hdmpz (120C) are formed compounds are insoluble in organic solvents. Their protonation of the 2 gives pyrazole-pyrazolate mononuclear complexes M (Hdmpz)2[(CF3)2pz]2 (M = Zn, Cu (3), Co (4)). Reaction of 1 with 3 and 4 under mild conditions lead to pyrazolate-bridged complexes with the cores Pd-M: Thus, these complexes can be used as building blocks to obtain more complex homo heterometallic complexes and clusters as analogues Phen or dipy. Acknowledgements- This work was supported by RFBR (projects 11-03-00824, 11-03-01157, 12-03-31339, 1303-90412) and the Presidium of the Department of Chemistry and Materials Science, Russian Academy of Sciences, and the Council for Grants of the President of the Russian Federation (MK-4452.2013.03) e-mail: snef@igic.ras.ru P62 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia QUANTUM CHEMICAL STUDY OF Au-CATALYZED REACTIONS OF SELECTIVE H-D EXCHANGE WITH THE SOLVENT IN QUERCETIN AND ITS OXIDIZED FORM N.G. Nikitenko, A.F. Shestakov The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432, Academician Semenov avenue 1, Chernogolovka, Moscow region, RUSSIA. Experimental data [1] show that H–D exchange in solution D2O – DMSO-d6 (1:4) of quercetin QcH2 and its oxidized form Qc occurs in 8-, 6- and 2’-positions (see Fig.). The exchange in the 2’-position takes place only in the presence of Au compounds. To understand the mechanism of reactions quantum chemical modeling was applied. All calculations have been performed by means of PRIRODA program using the nonempirical PBE functional and the extended basis set for SBK pseudopotential. It has been done using the facilities of Joint Supercomputer Center of the Russian Academy of Sciences. Calculation of the free energy of solvation was carried out in the Gaussian’03 program. QcH2 Qc Figure We investigated the energy profiles H–D exchange reactions in 8-, 6-, 2’-positions of QcH2 and Qc without gold complexes by the relayed mechanism involving water molecules (mechanism I) and the mechanism of electrophilic substitution involving Au complex (mechanism II). The activation energy of reaction by mechanism II is significantly reduced (~10 kcal/mol) when compared with that of the mechanism I in both cases. Thus, the most probable mechanism of H–D exchange in QcH2 and Qc with the solvent is II. The activation energy of reactions in the most favourable 8-position for QcH2 is 8.5 kcal/mol and for Qc is 7.9 kcal/mol. All the results obtained for the relative yield of H–D exchange products are in agreement with experiment. [1] A.F. Shestakov, A.V. Chernyak, N.V. Lariontseva, S.A. Golovanova, A.P. Sadkov, L.A. Levchenko, Mendeleev Comm , 2013, 23, 98-100. This work was supported by grant 12-03-31492 mol_a. e-mail: ng_nikitenko@mail.ru, a.s@icp.ac.ru P63 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Pd-POLYMER CATALYTIC SYSTEMS FOR CYANATION OF ARYL HALIDES WITH K4Fe(CN)6: ADAVANTAGES AND LIMITATIONS. O.M. Nikitin1,2, S.M. Masoud1, E.V. Zolotukhina3, M.A. Vorotyntsev1,3, T.V. Magdesieva1 1 Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1/3, Moscow, Russia 2 A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilova St. 28, Moscow, Russia 3 Institute for Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Semenov avenue 1, Chernogolovka, Moscow region, Russia Catalytic cyanation of aryl halides with K4Fe(CN)6 is very efficient and convenient due to low toxicity of cyanation agent. However, it requires Pd catalyst. Three types of catalytic system for cyanation of aryl halides using K4Fe(CN)6 were investigated:  Pd-polypyrrole nanocomposites (Pd/PPy) which were obtained via direct redox reaction between Pd(NH3)4Cl2 and pyrrole;  Carbon nanotubes with immobilized Pd nanoparticles covered with PPy matrix (Pd/PPy@CNt)  Pd-polymer complexes (based on polyamic acids containing biquinolyl coordinating units). HOOC HN COOH H N- O O n N N Pd2+ L L L = NMP, CH3CN Pd/PPy d(PPy) = 28 nm, 34wt.% of Pd d(Pd) = 1.4 nm, Pd/PPy@CNt d(Pd) = 1.6 nm 26 wt. % of Pd thickness of PPy layer = 10 nm Pd-polymer complex based on polyamic acids All three systems turned out to be active in cyanation of aryl halides with the use of K4Fe(CN)6 Pd/PPy can catalyze cyanation of a wide range of aryl halides, including arylchlorides. The reaction can be carried out with good to excellent yields of benzonitriles both in organic solvents (CH3CN, NMP), and in water. In the latter case the catalyst was immobilized on the graphite felt, to facilite its separation from the reaction mixture. Pd/PPy@CNt composites were less active in cyanatoin, probably due to fast sedimentation of their dispersion. However, prolonged heating of the reaction mixture (100°C, 20-25 hours) allowed to receive good yields for aryl iodides. Activation using microwave irradiation facilitates the reaction and allows to reduce reaction time up to 10-20 minutes. Due to the presence of nanotubes, the catalyst can be easily separated from the reaction mixture. The Pd polymer (based on polyamic acids) complexes were obtained via Pd anode dissolution in the presence of polymer ligand. This system can be used as in organicsolvents and water. The yield of benzonitriles was 70-90%. MW irradiation, as well as thermal activation, can be used to speed up of reaction the former being more efficient Acknowledgements. This work was supported by Russian Foundation for Basic Research (Project № 01203-00797) and Russian President Foundation (Project № MK-7093.2012.3) P64 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE REVEAL OF REGULARITIES OF ORIENTATION EFFECT OF SUBSTITUENT ON THE SUBSEQUENT SUBSTITUTION IN POLYHEDRAL [B12H12]2– CLUSTER A.I. Ogarkova, A.S. Chernyavskii, S.G. Sakharov and K.A. Solntsev a A.A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences, 119991, Leninskii av., 49, Moscow, RUSSIA Reactions of the following monosubstituted derivatives of dodecahydro-closo-dodecaborate (2–) anion were studied. Reaction of [B12H11I]2–, [B12H11OH]2–, [B12H11OC(O)CH3]2– and [B12H11SCN]2– with acetic acid in the presence of oxygen and atmospheric moisture. The single-stage procedure of the hydroxy group introduction into monosubstituted [B12H12]2– anion derivatives without the formation of acetoxo derivatives was developed. Reaction of [B12H11I]2–, [B12H11OH]2–, [B12H11OC(O)CH3]2– and [B12H11SCN]2– with formic acid in an inert atmosphere. Reaction of [B12H11I]2–, [B12H11OH]2– and [B12H11OC(O)CH3]2– with (SCN)2 solution in dichloromethane in an inert atmosphere. Reaction of [B12H11I]2–, [B12H11OH]2–, [B12H11OC(O)CH3]2– and [B12H11SCN]2– with dimethyl sulfoxide in the presence of acetic anhydride in an inert atmosphere. It was found for the reactions under consideration that substituents have the electron-seeking effect and decrease the reactivity of monosubstituted anions as compared to that of [B12H12]2–. The reactions under consideration were shown to have the regioselective character. The I, OH, OC(O)CH3 and SCN substituents are meta-orientants with respect to the introduced OH, OC(O)H and S(CH3)2 groups and the OH, OC(O)CH3 substituents are meta-orientants with respect to the introduced SCN group. In the case of the reaction of thiocyanogenation of monoiodosubstituted derivative of [B12H11I]2–, the 1,12-[B12H10I(SCN)]2– para-isomer is formed. It was found that the introduction of hydroxyl group into monosubstituted derivatives of [B12H12]2– increases substantially their water solubility as compared to that of non-substituted anion. Data on the synthesis of disubstituted derivatives of cluster [B12H12]2– boron anion and on the orientation effect of substituents can be used in developing BNCT preparations in the case of two biologically active substituents introduced into the boron skeleton of molecule. Acknowledgements The reported study was partially supported by RFBR, research project No. 12-03-31355 mol_a. e-mail: ogarkov_al@rambler.ru, solntsev@pran.ru P65 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE RESEARCH OF HYDROCARBON FRACTIONS COMPOSITION COMBUSTIONS UNDER THE ACTION OF CATALYSTS WITH ACTIVE METALOOXIDE ASSOCIATES Okhlobystin . ., Okhlobystina .V., Berberova N. ., Koldaeva Yu.Yu., Arefiev Ya.B. Astrakhan State Technical University, 414025, Tatischeva str, 16, Astrakhan, RUSSIA The activity of zeolite catalysts modified with nine-nuclear pivalates of transition metals (Ni, Co, Fe) with heat treatment was studied. The presence of the oxygen ( 3- ) and hydroxyl groups coordinated with metals in the structure of initial complexes promotes active metalooxide associates formation on the zeolite surface during termodestruction. The catalyst modified with nine-nuclear pivalate complex of nickel was studied in low-temperature light naphtha elevation process. The reaction was carried out at 200oC in inert gas atmosphere. It is studied that desulphurization process with hydrogen sulphide gassing take place during the reaction. It is established that amount of total sulphur decrease from 1040 wppm to 89 wppm. The same results were obtained in case of cobalt and iron complexes. Experiments at high temperatures (300-500 0 ) shows that naphtha undergoes catalytical combustions show in increased amount of liquid yield, decreased quality of total sulphur and cox. Acknowledgements e-mail: ionradical@gmail.com, sanikohl@gmail.com P66 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia 10 GROUP PINCER HYDRIDES (tBuPCP)MH (M=Pd, Ni): DIHYDROGEN BONDING AND PROTON TRANSFER REACTIONS E.S. Osipova, V.A. Kirkina, E.I. Gutsu, N.V. Belkova, O.A. Filippov, L.M. Epstein, E.S. Shubina a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilov Street 28, Moscow, RUSSIA Over the last decades there is a great interest to protonation of transition metal hydrides. Both classical polyhydrides and complexes with molecular hydrogen have been established to be the products of the proton transfer process. Yet, protonation is the most convenient way to obtain 2-H2 complexes. However, most of these complexes of the Group 10 metals are very unstable. The key role of dihydrogen bonded intermediates (MH···HX) in formation of non-classical cationic hydrides was shown [1]. But still there is no enough information about the intermediates of the 10 group metal hydrides protonation [2]. PtBu2 M H PtBu2 In this work the interaction between tridentate pincer 10 group metal hydride complexes L3MH (M = Ni, Pd, L3 = 2,6-(CH2P(t-C4H9)2)2C6H4 (PCP, and proton donors of different strength and nature (RFOH = (CF3)nCH3-nOH, n = 13, indole, p-nitrophenols, CpM(CO)3H) was studied by IR ( MH, CO and OH) and NMR (1H, 31P, 195Pt) and UV-vis spectroscopy in a wide temperature range (190-290 K). The products and intermediates of the interaction were established. The peculiarities of their structure are revealed by DFT calculations. Kinetic and thermodynamic parameters of hydrogen bonding and proton transfer accompanied by H2 evolution will be compared. Remarkable finding is the difference in the structure of the protonated reaction intermediate, which is the “traditional” 2-H2 species in case of ROH acids, but the unconventional , 1:1-H2 species featuring an end-on coordination of dihydrogen between the two transition metals in case of MH acids. Acknowledgements - this work was supported by the Division of Chemistry and Material Science of RAS and RFBR (11-03-01210, 12-03-33018), and CNR-RAS bilateral agreement. [1] N. V. Belkova, E. S. Shubina, and L. M. Epstein, Eur. J.Inorg. Chem., 2010, 3555. [2] V. A. Levina, A. Rossin, N. V. Belkova, M. R. Chierotti, L. M. Epstein, O. A. Filippov, R. Gobetto, L. Gonsalvi, A. Lledós, E.S. Shubina, F. Zanobini, and M. Peruzzini, Angew. Chem. Int. Ed., 2011, 50, 1367. P67 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CHEMICAL DESIGN OF CHALCOGEN-CONTAINING ORGANOMETALLIC CLUSTERS A.A. Pasynskii, Yu.V. Torubaev, I.V. Skabitsky, S.S. Shapovalov, A.V. Pavlova N.S.Kurnakov Institute of General and Inorganic Chemistry, Moscow,Russia aapas@rambler.ru The chalcogen-containing organometallic complexes were used as ligands to complexes of different transition metals (M). X-Ray analyses data showed the common features: a) sharp shortening (from 0.15 to 0.3 A) of formally ordinary M-E bonds (E = S, Se, Te) and M-P bonds[1] compared to the covalent radii sum (CRS) [2] ; b) electron-compensating rearragment of clusters. 1. The coordination of Fc2Te2 (Fc – ferrocenyl) and dissociation of Te-Te bond: Fc UV hexane, -10o C Te M(CO)4 (OC)4M -2CO Te M=Cr, Mo, W Fc 2. The coordination of CpFe(CO)2TePh. Fe+ OC Fe OC Fe Te Te CO OC CO CO CpFe(CO)3+ ClRe(CO)3(THF)2 THF - 2CO Te OC Fe Cl 3. The coordination and transmetallation of [CpMn(CO)2]2E2 (E = S, Se, Te) [CpMn(CO)2]2(E2) Cr(CO)5(THF) [CpMn(CO)2]2(E2)[Cr(CO)5]2 (PPh3) 2Pt(Ph2C2) (PPh3 )2 Pt(Ph2C2 ) Mn CO I CO Ph3P MnI E II Pt PPh3 E CO I CO Mn CO CO Ph3P II Pt S S CO OC PPh3 Cr CO CO CO [1]. A.A. Pasynskii , Russ. J. Coord. Chem., 2011, Vol. 37, No. 11, p. 801 [2]. Cordero, B., Gomez, V., Platero-Prats, A.E., et al., Dalton Trans., 2008, p. 2832 P68 CO Re Fe OC 2 CpFe(CO)2TePh CO Te CO CO International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ORGANOTELLURIUM METALLILIGANDS AS A BUILDING BLOCKS A.V. Pavlovaa, Yu.V. Torubaeva a Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences,11999, Leninsky prospect 31, Moscow, RUSSIA. In this work we investigate the approaches to the directed synthesis of metal carbonylchalcogenide complexes as a precursors of inorganic materials using organotellurium metalliligands as a building blocks. CpFe(CO)2TePh gives bimetallic complex CpFe(CO)2( -TePh)Fe(CO)4I2 on interaction with Fe(CO)4I2 and trimetallic 5-membered chain cluster (CpFe(CO)2( TePh))2Re(CO)3Cl on interaction with Re(CO)3(THF)2Cl. In the homo-metallic CpFe(CO)2( -TePh)Fe(CO)2I2 both Fe-Te distances are shortened but not equal. Fe(Cp)…Te distance (2.569 Å) is shorter than 2.612Å for Fe-Te distance of Fe(CO)3I2 fragment (and as compared to 2.617Å Fe-Te in the starting CpFe(CO)2TePh [2]. This results from the different back-donative ability of {CpFe(CO)2} vs {Fe(CO)3I2} fragments. Hetherometallic (CpFe(CO)2( -TePh))2Re(CO)3Cl reveals the same shortening of Te…Re (2.816 Å) (r(Re/Te)=2.89 Å),and Te…Fe (2.571 Å) distances. Further treatment of (CpFe(CO)2( -TePh))2Re(CO)3Cl with dppePtCl2 eliminates CpFe(CO)2TePh ligand giving Pt/Re complex with two PhTe bridges. The distance Te…Re (2.784 Å) is shorter than the sum of the covalent radii (r(Re/Te)=2.89 Å) and Pt…Te distance (2.632 Å) is shorter too compared with the sum of the covalent radii (r(Pt/Te)=2.74 Å). [1] . B. Cordero, V. Gґomez, A. E. Platero-Prats, M, Revґes, J. Echeverrґıa, E. Cremades, F Barragґan and S. Alvarez // Dalton Trans., 2008, 2832–2838. [2] Torubaev Yu.V., Pasynskii A.A., Skabitskii I.V.// Russian Journal of Coordination Chemistry. 2009. . 35. № 5. . 341-346. Acknowledgements – RFBR (Grant No. 12-03-33101) e-mail: alinca.star@gmail.com P69 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia (CO)POLYMERIZATION OF VINYL NOMERS IN THE PRESENCE OF IRON COMPLEXES M. Pavlovskaya, D. Grishin a Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina prosp, 23, Nizhny Novgorod, RUSSIA. Novel polymer materials are demanded in different areas of modern technology and industry. The synthesis of block-, graft- and brushed copolymers significantly increases the range of polymer properties and opens novel applications. The use of organometallic compounds for precise polymer synthesis is perspective division in modern polymer chemistry. In this work the peculiarities of vinyl chloride (VC) polymerization in the presence of iron carbonyl complexes with different ligand environment ([CpFe(CO)2]2, CpFe(CO)2Br, CpFe(CO)2Cl] were investigated. Different organic halides (carbon tetrachloride, isoamyl iodide and ethyl-2-isobutyrate) were used as co-initiators. It was established that binuclear iron complex in conjunction with carbon tetrachloride act as initiator-regulator of VC polymerization. The poly(vinyl chloride) obtained in mentioned conditions may be further used as a macroinitiator for synthesis of copolymers with methyl methacrylate, styrene and vinyl acetate. The graft-copolymers are perspective materials as their properties strongly demand on main and side chains length, composition and so on and thus may be changed in wide range. The graft copolymers of polystyrene with poly(methyl methacrylate) and poly(vinyl acetate) were synthethised in the presence of iron carbonyl complexes ([CpFe(CO)2]2, CpFe(CO)2Br, CpFe(CO)2Cl]) and with the use of Fe(0) with PPh3 as a catalytic system. A brominated polystyrene obtained by Fridel-Krafts reaction was used as a macroinitiator. The efficiency of monomer graft and yield were measured and compared. It was shown that the most effective system for methyl methacrylate graft polymerization was one based on CpFe(CO)2Br. The best results for synthesis of poly(vinyl chloride) – polystyrene and polystyrene – poly (vinyl acetate) were obtained in the presence of binuclear iron complex. The molecular weight parameters, composition and some physico-chemicals properties of obtained copolymers were measured. Acknowledgements - This work was supported Russian Ministry of Education and Science (“Federal target program of scientific and scientific-pedagogical personnel of innovation of Russia on 2009-2013”) and Russian Foundation of Basic Research (pr. 11-03-00074). e-mail: pavlovskaya@ichem.unn.ru P70 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE REACTIVITY OF NON-TRANSITION METAL O-AMIDOPHENOLATE COMPLEXES TOWARDS ALKYL HALIDES A.V. Piskunov, I.N. Meshcheryakova, I.V. Ershova, M.G. Chegerev G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The search of new highly selective reactions of C-C bond formation is one of the primary goals in the organic chemistry. In present time it is achieved quite effectively by using of metal complex catalysis. The noble transition metal (Pd, Rh, Pt, etc.) derivatives play a dominant role in catalytic carbon-carbon (or carbon-heteroatom) bond formation. It can be explained by the ability of such compounds to participate readily in one-step two-electron transfer processes which are elementary steps of numerous transition metal catalyzed transformations. The complexes of the first-row transition metals are mostly characterized by one-electron transformations and have a less application in homogeneous catalysis. It is true for main group metal compounds for which the processes of electron transfer are unusual at all. The problem of inactivity of these elements in multiple electron transformations may be solved by means of the insertion of redox active ligands in their coordination sphere. The present work is the investigation of potential participation of non-transition metal complexes containing redox active ligands in the cross-coupling reactions, in particular the possibility of alkyl halides activation by such type compounds. The non-transition metal complexes of the type [AP2M]Na were found to react readily with different alkyl halides (Scheme). The reaction proceeds at mild conditions and leads to new metal derivatives containing iminocyclohexa-1,4-dienolate ligands. The reaction involving indium complexes with less hindered o-amidophenolate ligands leads to deeper alkylation of the forming redox active ligand. Acknowledgements - We are grateful to the FSP ‘‘Scientiﬁc and Scientiﬁc-Pedagogical Cadres of Innovation Russia’’ for 2009–2013 years (GK 8465), Russian Foundation for Basic Research (grant 13-03-97048r_povolzh’e_a), Russian President Grants (NSh-1113.2012.3) for financial support of this work. e-mail: pial@iomc.ras.ru P71 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NORBORNENE-BASED SILICON-CONTAINING POLYMERIC MATERIALS. SINTHESIS, LUMINESCENT PROPERTIES E.O. Platonova, G.V. Basova, Yu.P. Barinova, I.K. Grigorieva, E.V. Baranov, L.N. Bochkarev G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The norbornene derivative with Ph3Si functional group was synthesized and structurally characterized. The obtained functionalized norbornene monomer was found to enter into ROMP reactions and produce the silicon-containing polymeric materials. Mw = 41000 PDI = 2.2 Tg = 170oC SiPh 3 poly(NBE-SiPh3) n m n N SiPh 3 m:n = 1:1 poly(NBE-SiPh3 -NBE-carb) M w = 31100 PDI = 1.8 T g = 158o C Photophysical properties of the synthesized compounds were investigated. The monomer compound and polymeric materials were found to reveal photoluminescence (PL) of blue color. 1000 1000 PL intensity (a.u.) PL intensity (a.u.) poly(NBE-SiPh3) 800 600 400 200 poly(NBE-SiPh3-NBE-carb) 800 600 400 200 0 0 350 400 450 500 Wavelength (nm), ex = 320 nm 550 350 400 450 500 Wavelength (nm), ex = 320 nm 550 The relative PL quantum yields of NBE-SiPh3 (6%), poly(NBE-SiPh3) (7%) and poly(NBESiPh3-NBE-carb) (14%) were determined in CH2Cl2 at room temperature (reference anthracene in EtOH (Ø =27%)). Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Project No. 1303-97051 r_povolzje_a) e-mail: platonova@iomc.ras.ru P72 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE COMPLEXES OF MAIN GROUP METALS BEARING REDOX ACTIVE LIGANDS: THE REVERSIBLE BINDING OF O2 AND NO A. Poddel’skya, E. Ilyakina, N.A. Protasenko, I.V. Smolyaninovb, G.K. Fukin, N.T. Berberovab, V. Cherkasov and G. Abakumov a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. It is well known that both molecular oxygen and nitrogen oxide(II) play an important role in chemical and biochemical processes. Until recently, the range of compounds capable of fixing these small molecules was limited almost completely to transition metal compounds. Until recently main group metal complexes capable to reversible binding of O2 and NO were not known. The combination of nontransition metal with redox-active ligand allows to construct the system which will be able to model the chemical behaviour of transition metal complexes. We have found that antimony(V) o-amidophenolates and some catecholates react reversibly with molecular oxygen in mild conditions to yield spiroendoperoxides [1]. This ability is affected by the redox-properties of O,O- or O,N-chelating redox-active ligands as well as the acceptor/donor/shielding properties of substituents at the central antimony atom [1,2]. The II group metal catecholates are easily oxidized by NO to corresponding o-semiquinonatonitrosyl derivatives which are detectable by EPR [3]. At low temperature zinc(II) and cadmium(II) bis-o-semiquinolates/o-iminosemiquinolates react reversibly with NO in toluene/hexane solution to give corresponding (SQ)(Q)M(NO) complexes. tBu tBu O N O N O O2 N O O SbR3 SbR3 N O tBu tBu tBu tBu O NO, THF O Pb O O tBu tBu N Zn O O tBu tBu Ar tBu N NO Pb NO t tBu tBu tBu Ar NO Zn Ar N N O Ar But O tBu [1] A.I. Poddel’sky, I.V. Smolyaninov, Yu.A. Kurskii, G.K. Fukin, N.T. Berberova, V.K. Cherkasov, G.A. Abakumov, J. Organomet. Chem., 2010, 695, 1215-1224. [2] G.K. Fukin, E.V. Baranov, A.I. Poddel´sky, V.K. Cherkasov, G.A. Abakumov, ChemPhysChem, 2012, 13, 3773-3776. [3] E.V. Ilyakina, A.I. Poddel’sky, V.K. Cherkasov, G.A. Abakumov, Mendeleev Commun., 2012, 22, 208-210. Acknowledgements - We are grateful to the Russian Foundation for Basic Research (grants N 13-3-01022, 1103-00389, 12-03-31367, 12-03-31026, 13-03-97048 r_povolzh’e_a), President of Russian Federation (grants NSh-1113.2012.3) for financial support of this work. This work was made according to FSP “Scientific and scientificpedagogical cadres of innovation Russia” for 2009e2013 years (Contract 8465 from 31.08.2012). e-mail: aip@iomc.ras.ru P73 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SEMIQUINONATE AND CATEHOLATE METAL COMPLEXES WITH FORMAZAN LIGANDS N.A. Protasenkoa, A.I. Poddel’skya and A.S. Bogomyakovb a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA b International Tomography Center SD Russian Academy of Sciences, 630090, Institutskaya str, 3a, Novosibirsk, RUSSIA Formazanes are the compounds which contain the characteristic azo-hydrazone bond system. They are known as the chelating π-conjugated N-donor ligands. The denticity of those ligands may be controlled by means of variation of substituents (R1, R2, R3) and inclusion of additional complexing groups. Owing to this fact formazanes hold promise in the preparation of molecularly designed metal complex systems. Formazanes and their metal complexes are widely used in chemistry as analytical reagents, environmentally-friendly colorants, solar cells and thermosensitive elements. Ph Ph R3 3 C R1 2 1 N N Ph t-Bu O H N N 4 5 Formazane N N R5 N HN M O t-Bu Ph O t-Bu Ph N HN N N N t-Bu O M O O t-Bu M = CoII, MnII, Fe II t-Bu O t-Bu O t-Bu M = CoIII, MnIII In the present work we have synthesized a series of 3,6-di-tert-butyl-o-benzosemiquinonato cobalt and manganese complexes with formazan ligands (such as 1,3,5-triphenylformazane, 3-(4’-pyridyl)-1,5-diphenylformazane, 1-(2,6-dimethylphenyl)-3-(4’-pyridyl)-5-phenylformazane, 5-(4’-fluorophenyl)-1,3-diphenylformazane, 5-(4’-iodophenyl)-1,3-diphenylformazane). Complexes were characterized by IR, NIR spectroscopy and elemental analysis. Magnetic susceptibility measurements carried out for cobalt and manganese complexes with 1,3,5triphenylformazane and 3-(4’-pyridyl)-1,5-diphenylformazane have shown that cobalt complexes contain the metal in low-spin state, whereas it is in the high-spin state in the corresponding manganese compounds. Acknowledgements - We are grateful to RFBR (N 2013-3-01022, 13-03-00891 and 12-03-31367 mol_a), President of Russian Federation (Grant NSh-1113.2012.3) for financial supporting of this work. This work was performed in the accordance with FSP (contract N8465 from 31.08.2012). e-mail: tessun@yandex.ru, aip@iomc.ras.ru P74 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COMPLEXES OF REDOX-ACTIVE RIGID QUINONEIMINE LIGAND (DPP-QIAN) D. Razborov, I. Fedushkin and A. Lukoyanov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Acenaphthene-1,2-quinoneimine (dpp-QIAN, 1) was obtained by partial condensation of 2,6diisopropylaniline with acenaphthenequinone (Scheme 1). O ArNH2 O MeOH HCOOH O N Ar 1 i-Pr Ar = i-Pr Scheme 1. Synthesis of acenaphthene-1,2-quinoneimine (1). Fig. 1 The crystal structure of compound 1 Crystals of compound 1 suitable for X-ray diffraction were obtained from Et2O. Due to steric constraints of i-Pr-groups there is no rotation of aryl substituent along Cipso–N bond. Therefore, the most favourable orientation of the aryl substituent is an orthogonal orientation relative to the acenaphthene plane (Fig. 1). Magnesium complexes with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) are the most studied. Similarly we have carried reduction dpp-QIAN with magnesium metal in THF. The reaction product (dpp-QIAN)Mg(THF)3 (2) was isolated as blue-green crystals with the yield of 80%. Complex 2 reacts with allyl bromide with the formation of the adduct which structure was proved clearly by 1H-1H COSY NMR spectroscopy. In contrast to (dppBIAN)Mg(THF)3 the complex 2 does not react with phenylacetylene and benzophenone. The product of the reaction of dpp-QIAN with the metallic europium was isolated as deep-green crystals. X-ray diffraction studies proved the tetrameric structure of aimed complex [(QIAN)Eu]4(THF)4(DME). The reduction of the dpp-QIAN with excess of sodium and potassium accompanied with change of color of the reaction mixture. Complexes (dpp-QIAN)Na4(THF)n and (dppQIAN)K4(THF)n were isolated as orange and brown crystals. The attempts of reducing of dpp-QIAN with calcium and samarium led to the formation of intensively coloured solutions, but no crystalline products were isolated. Also, we carried the reactions with various chlorides, i.e. ZnCl2, GaCl3. The reaction of dpp-QIAN with zinc chloride (II) give [(dppQIAN)ZnCl2]2 which was isolated as orange crystals stable in air. For one's turn gallium chloride (III) reacts with dpp-QIAN with the formation of bisligand complex [(dppQIAN)2GaCl2]+[GaCl4]-. It is known that symmetrical dpp-BIAN and gallium chloride (III) forms an ionic complex [(dpp-BIAN)GaCl2]+[GaCl4]-. Acknowledgements – Work was supported by the Russian Foundation for Basic Research (Grants № 12-0301016-a). e-mail: razborov@iomc.ras.ru, igorfed@iomc.ras.ru P75 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND LUMINESCENCE PROPERTIES OF POLYMERIC TERBIUM COMPLEXES WITH PYRAZOLONATE LIGANDS A.V. Rozhkov, L.N. Bochkarev, V.A. Ilichev G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The new heteroligand terbium complex Tb(PMIP)2PyrNBE·2Ph3PO was prepared by reaction of terbium chloride with sodium salts of PMIP (4-isobutyryl-3-methyl-1-phenyl-1H-pyrazol5(4H)-one) and PyrNBE (4-(bicyclo[2.2.1]hept-5-ene-2-carbonyl)-3-methyl-1-phenyl-1Hpyrazol-5(4H)-one) in the presence of triphenylphosphine oxide: The resulting compound was isolated in yield 91% and characterized by IR spectroscopy and elemental analysis. Photoluminescence (PL) spectra of the complex in solution and thin film consist of emission bands of Tb3+ ion. The polymeric terbium complexes P1-P3 was prepared by metathesis copolymerization of Tb(PMIP)2PyrNBE·2Ph3PO with carbazole-functionalized norbornene monomers: 2 The copolymerization reactions were carried out at room temperature and completed in 6-8 hours. Polymeric complexes were isolated in high yields (83-92%) and characterized by elemental analysis, IR, GPC, DSC (Mw= (2.1-3.8)·104, PDI = 1.29-1.80, Tg = 156-172°C). They exhibited metal-centered emission in PL and electroluminescent spectra. The OLED device with the configuration of ITO/P1/BATH/Alq3/Yb produced green light with the maximum brightness of 70 cd/m2. e-mail: iomcrozhkov@gmail.com P76 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS, STRUCTURES AND SOME PROPERTIES OF LANTHANIDE 4-ACYLPYRAZOLONATE COMPLEXES A. V. Safronova, L. N. Bochkarev and E. V. Baranov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. It was found that 4-acylpyrazolones R-PMPH (R = Pri, But, CHEt2) react with metallic lanthanides in THF solution in the presence of catalytic amount of LnI3 and form lanthanide pyrazolonates Ln(R-PMP)3 in almost quantitative yields: Ln = Y, Pr, Nd, Gd, Tb, Ho, Er, Tm The compounds Ln(R-PMP)3 (R = Pri, But, CHEt2) were found to sublime in vacuum (10–3 Torr) without decomposition in the temperature range of 230-270°C. Single crystal X-ray analyses of the sublimed complexes Ln(R-PMP)3 (R = Pri, But) revealed dimmers [Ln(RPMP)3]2 in which rare-earth metals are bridged by pyrazolonate units. The coordination environment of the metal atoms can be described as distorted monocapped trigonal prism. Novel 4-perfluorobenzoylpyrazolone PhF-PMPH was synthesized in 80% yield by the reaction of 1-phenyl-3-methyl-5-pyrazolone with pentafluorobenzoyl chloride in THF solution in the presence of calcium hydroxide. The 4-acylpyrazolone PhF-PMPH reacts with lanthanide amides Ln[(Me3Si)2N]3 (Ln = Eu, Tb, Yb) and forms the lanthanide pyrazolonates Ln(PhF -PMP)3 in high yields. All the synthesized compounds were characterized by elemental analysis and IR spectroscopy. The diamagnetic yttrium and lutetium derivatives have been also studied by NMR. Acknowledgements - This work was supported by the Russian Foundation for Basic Research (project no. 1203-00250_a e-mail: san@iomc.ras.ru P77 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia BIVALENT IRON, COBALT AND NICKEL COMPLEXES OF 1,10-PHENANTHROLINE AND 2,2´-BIPYRIDYL WITH THE CLOSO-BORATE ANIONS BnHn2- (n = 10, 12) E. Safronovaa, V. Avdeevaa, A. Vologzhaninab, L. Goevaa, E. Malininaa, N. Kuznetsova a Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky prospect, 31, Moscow, RUSSIA b Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilova str, 28, Moscow, RUSSIA Complexes of general formula [MIIL3]BnHn·xH2O (MII = Co or Ni; L = phen or bipy; n = 10, 12; x = 1, 2) identified by elemental analysis and IR-spectroscopy are known [1-3]. Thus, nickel(II) complexes [NiL3]BnHn was obtained by interaction of water solutions of NiCl2 with Cs2BnHn (n = 10, 12) with azaheterocyclic ligands L solved in ethanol [1]. The same cobalt(II) complexes [CoL3]BnHn was obtained when (H3O)2BnHn was allowed to react with Ba(OH)2 and the obtained barium closo-borate interacts with sulfates of the corresponding metals and then with ligands [2-3]. All the mentioned complexes were obtained as precipitates from H2O / C2H5OH solutions and could not be prepared in crystalline form. This procedure for synthesis of the complexes is not convenient because it requires preparation of the corresponding acids (H3O)2BnHn from (Et3NH)2BnHn by anion exchange column and then isolation of the corresponding cesium or barium salts. At the same time, syntheses from (Et3NH)2BnHn are preferable because in this form the closo-borate anions are obtained from decaborane-14. In this work we prepared a number of M(II) complexes (M = Fe, Co, Ni) with the closo-borate anions and phen or bipy [MIIL3]BnHn. The obtained complexes were investigated by elemental analysis, IR- and UV-spectroscopy, X-ray crystallography. We broadened the list of complexes by preparation of iron(II) complexes that had not been mentioned in the literature. The complexes were prepared in CH3CN or DMF solutions by the simple one-step reactions when (Et3NH)2BnHn was allowed to react with MCl2 (M = Fe, Co, Ni; n = 10, 12) in the presence of 3 equiv. of phen or bipy. In this case, the obtained complexes formed as monocrystals useful for X-ray diffraction analysis. Structure of [Fephen3]B10H10·DMF is presented in the picture. According to the obtained data, all the compounds contain cationic complexes [ML3]2+ (M = Fe, Co, Ni) and closo-borate anions as counterions. In some cases, BH-groups form specific interactions wih H-atoms of the solvent molecules presented in crystals. The obtained complexes are interesting from the point of view both of inorganic and bioorganic chemistry. [1] Yu. Gaft, N. Kuznetsov, L. Sukova, Russ. J. Inorg. Chem., 1983, 28(1), 162-167. [2] A. Kayumov, A. Yakushev, K. Solntsev, et al., Russ. J. Inorg. Chem., 1988, 33(10), 2587-2593. [2] A. Kayumov, K. Solntsev, L. Goeva, et al., Russ. J. Inorg. Chem., 1988, 33(8), 1936-1942. This work was supported by the Russian Foundation for Basic Research (project no. 12-03-31173) and Council of the President of the Russian Federation (grant MK-1728.2013.3). e-mail: safronova.ef@gmail.com, avdeeva.varvara@mail.ru, malinina@igic.ras.ru P78 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REVERSIBLE BINDING OF MOLECULAR OXYGEN TO CATECHOLATE AND AMIDOPHENOLATE COMPLEXES OF SB(V): ENERGY ASPECTS M.A. Samsonova, G.K. Fukina a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Recently, it was found that catecholate and amidophenolate complexes Sb(V) can reversibly binding of molecular oxygen [1, 2]. We have shown, that ability of these complexes to bind oxygen depends on electronic (-5.09 (inert) <EHOMO < -5.06 (inert)) and steric factors (G< 90%) [3, 4]. Herein we would like to focus out attention to energy aspects reactions of such type. DFT calculations have been performed for Sb(V) (1) (p-F-Ph)3Sb(3,6-But-Cat), (2) (p-Me-Ph)3(6-Br-3,5-But-Cat)Sb, (3) (p-Me-Ph)3(6-Cl-3,5-But-Cat)Sb, (4) Ph3SbCat, (5) Ph3(3,6-But-Cat)Sb, (6) (o-Me-Ph)3(3,6-But-Cat)Sb, (7) (p-Me-Ph)3(3,6-But-Cat)Sb, (8) t Ph3(3,6-Bu -4,5-N2C4H6-Cat)Sb, (9) Ph3(3,6-But-4-OMe-Cat)Sb, (10) t Ph3(3,6-Bu -4,5-OMe-Cat)Sb, (11) Ph3(2,6-Pri-Ph-AP)Sb, (12) (o-MePh)3(2,6-Pri-Ph-AP)Sb, (13) Ph3(2,6Me-Ph-AP)Sb, and [R3SbCatO2]vdw, [R3SbCatO2]ts, [R3SbCatO2]sp complexes (Figure 1). It was shown, that evaluation of ΔEA1, ΔEA2, ΔER1, ΔER2, allows to explain behavior the complexes relative to oxygen (-7.023(act.) < ΔER1 < -4.365(in.), -4.962(act.) < Figure 1. Reaction scheme ΔER2 < -2.278(in.) kcal / mol). vdw sp – van der Waals and spiroendoperoxide Besides we have analyzed the complexes , ts – transition state energy of intramolecular interactions for [R3SbCat·O2]vdw complexes according R. F. W. Bader theory. These criteria allow to evaluate the activity of Sb(V) complexes in reactions reversible binding of molecular oxygen. 1. G. A. Abakumov, A. I. Poddel’sky, E. V. Grunova, V. K. Cherkasov, G. K. Fukin, Yu. A. Kurskii, L. G. Abakumova, Angew. Chem. 2005, 117, 2827 – 2831; Angew. Chem. Int. Ed. 2005, 44, 2767 –2771 2. V. K. Cherkasov, G. A. Abakumov, E. V. Grunova, A. I. Poddel’sky, G. K.Fukin, E. V. Baranov, Yu. A. Kurskii, L. G. Abakumova, Chem. Eur. J. 2006, 12, 3916 –3927 3. G.K. Fukin, E. V. Baranov, A. I. Poddel’sky, V. K. Cherkasov, G. A. Abakumov, ChemPhysChem 2012, 13, 3773 – 3776 4. Georgy K. Fukin, Evgenii V. Baranov, Christian Jelsch, Benoît Guillot, Andrey I. Poddel’sky, Vladimir K. Cherkasov, and Gleb A. Abakumov, J. Phys. Chem. A 2011, 115, 8271–8281 Acknowledgements - This work was supported by the Russian Foundation for Basic Research (grants № 13-03-00891 and № 12-03-31865) e-mail: max@iomc.ras.ru P79 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND PROPERTIES OF 2-HETARYL-3-HYDROXYBENZOIC ACID ESTERS Yu. .Sayapina,b, I. O. Tupaeva , A.A. Kolodina ,b, S.A. Nikolaevskii , N.I. Makarova , V. V. Tkachevc, S. M. Aldoshinc, V. I. Minkin ,b a Institute of Physical and Organic Chemistry of Southern Federal University, 344090, 194/2 Stachka St, Rostov on Don, RUSSIA. b Southern Scientific Center of Russian Academy of Sciences, 344006, 41 Chehova St, Rostov on Don, RUSSIA. Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432, 1 Akad. N.N. Semenova Av, Czernogolovka, RUSSIA. The interaction of 2-methylbenzoxo(thia)zoles with -chloranyl leads to 2-hetaryl-2-ylsubstituted 1,3-tropolones 1. The structural peculiarity of 1,3-tropolones 1 is the presence of a strong intramolecular hydrogen bond in the six-membered chelate ring. In most of the cases the proton signal of the OH group in the 1H NMR spectra is present in the weak field (18-20 ppm in the form of a broad singlet), that correlates with the strength of the - ···N hydrogen bond. According to the X-ray data the distance O – N comprises 2.480 - 2.534 Å. As a result, the classic complex formation reactions of the compounds 1 with transition metal ions are virtually impossible. We determined that boiling of 1,3-tropolones 1 in alcohols ( OH, EtOH, i-PrOH) is accompanied by isomerization with formation of derivatives of 3-hydroxybenzoic acid esters 2,3 (Scheme 1). Scheme 1 X O Cl N H O Cl R X R1OH Cl 1 a) R1 = Me b) R1 = Et c) R1 = i-Pro X=O, S. O OR1 X Zn(OAc)2 Cl N H O 2,3 Cl O OR1 Cl N 2R=H 3 R = Cl R 2 Zn O Cl 4 R The solutions of compounds 2,3 demonstrate an intensive luminescence and we determined the spectral absorption and fluorescent properties of 2-(2'-hydroxyphenyl))benzoxazoles 2,3. Under irradiation of 2-(2'-hydroxyphenyl))benzoxazoles 3a-f in heptane ( irr=365 nm) at T=293 K there occurs an excited-state intramolecular proton transfer (ESIPT) O−H…N → O…H−N (from enol form to keto form), which results in formation of an emitting NHstructure in the excited state. The quantum yields of fluorescence are 0.18 – 0.20 for 2,3. We are synthesized Zn(II) complexes on the base of 2-(2'-hydroxyphenyl))benzoxazol ligands 2,3. The structures of the obtained compounds 1-4 are confirmed by elemental analysis, and NMR 1 H, IR-spectroscopy, and mass-spectrometry data. The molecular structures of the key compounds are determined by x-ray methods. Acknowledgements – The work was financially supported by the grants of the President of the Russian Federation (grant Nos. MK-4215.2012.3 and NSh-927.2012.3), by the Russian Foundation for Basic Research (project no. 12-03-31491-mol-a, 12-03-31285-mol-a) and by the RAS presidium programme “Development of the methods of obtaining new chemical substances and creation of new materials”. e-mail: a. boom@ipoc.rsu.ru, b. sayapin@ipoc.rsu.ru, c. vatka@icp.ac.ru P80 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia PGSE NMR STUDY OF TRIPHENYLANTIMONY(V) CATECHOLATES INTERACTION WITH SMALL MOLECULES IN SOLUTION A.S. Shavyrin, A.I. Poddel’sky G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Pulsed Gradient Spin Echo (PGSE) Nuclear Magnetic Resonance is the method for determining mobility of molecules in liquid by NMR. Using Pulsed Field Gradients (PFG) in conjunction with specific NMR pulse program leads to attenuation of NMR signals proportionally to molecules mobility in a solution. This mobility relies on diffusion coefficient which is dependent on hydrodynamic radius of molecule, viscosity of solvent and temperature - the properties of dissolved molecule and its surrounding environment. The analysis of resulting PGSE and Diffusion Ordered SpectroscopY (DOSY) NMR spectra isn’t straightforward but processing the series of obtained spectra lets to quantitatively determine molecules interactions in solution. Triphenylantimony(V) catecholates attracts considerable interest due to their ability of reversible oxygen binding and some other promising properties. According to X-Ray studies antimony(V) catecholates are often contain small molecules of solvent in crystal phase, but is this interaction observable by diffusion NMR in solution? Is it possible to determine quantity of interacting molecules by NMR? In this work we have applied 1D PGSE and 2D DOSY methods to study the interaction of triphenylantimony(V) catecholates with various small molecules (diethyl ether, THF, pyridine, acetone) in solution. Obtained diffusion coefficients and their dependence on concentration, molecular weight and nature of interacting molecules is discussed. Acknowledgements - This work was supported by the grant of President of Russian Federation ( NSh1113.2012.3) e-mail: andrew@iomc.ras.ru P81 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NANOMETALLOCARBOSILANES AND ORGANOELEMENTOXANES AS ORGANOMETALLIC PRECURSORS OF PROMISING CERAMIC COMPOSITES COMPONENTS G. Shcherbakovaa, M. Varfolomeeva, T. Movchana, D. Zhigalova, D. Sidorova, G. Yurkovb a SSC RF Federal State Unitary Enterprise “State Research Institute for Chemistry and Technology of Organoelement Compounds”, 105118, shosse Entuziastov, 38, Moscow RUSSIA. b : A.A. Baikov Institute for Metallurgy and Material Science of Russian Academy of Science , 119991, Leninskiy pr., 49, Moscow, RUSSIA. One of the most promising approaches to the creation of modern nanostructured ceramic materials with specific properties (high strength, high temperature and oxidation resistant ceramic composites) is to use preceramic oligomers and polymers as starting materials. The authors have developed highly efficient methods of synthesis and studied the characteristics of the molecular structure of preceramic organometallic poly(oligo)mers nanometallocarbosilanes [1,2] and organoelementoxanes [3-5]. The process of introducing nanoparticles of refractory and magnetic metals, homogeneous distribution of the particles in a nonmagnetic carbosilane matrix was investigated. The processes of thermochemical transformation of the synthesized nanometallocarbosilanes samples into silicon carbide SiC, modified by nanoparticles of refractory compounds (Zr; Hf; Ta) or magnetic metals (Fe; Co); organoalumoxanes in corundum α-Al2O3, organoalumoxansiloxanes into mullite 3Al2O3•2SiO2, organoyttriumoxanalumoxanes into the ceramic composition Al2O3•Y2O3 (particularly YAG 5Al2O3•3Y2O3) and organoyttriumoxanalumoxansiloxanes in the ceramic composition: Al2O3•Y2O3•SiO2 were studied. It is known that SiC is a very tough, durable material that is thermally and chemically resistant, its sintering requires high temperature and pressure. The use of sintering additive Al2O3•Y2O3 or Al2O3•Y2O3•SiO2 reduces the sintering temperature and allows us to obtain a dense ceramic material for constructional purposes. The introduction of cobalt ferrite nanoparticles in polycarbosilane space was studied. Calcinating of a composite to 800° resulted in polycarbosilane transformation in amorphous silica in which volume cobalt ferrite nanoparticles were localized. By means of TEM and XRD methods, we demonstrated that nanoparticles represent cobalt metal with cubic structure. The cobalt ferrite nanoparticles were found to have the average size of 20 nm. Based upon the foregoing data we suggest that the composite has the properties of a weak ferromagnetic [6]. [1] P.A. Storozhenko, G.I. Shcherbakova, A.M. Tsirlin, E.K. Florina, E.A. Izmailova, A.A. Savitskii, M.G. Kuznetsova, T.M. Kuznetsova, I.V. Stolyarova, G.Yu. Yurkov, S.P. Gubin, Inorganic Materials, 2006, 42, 10, 1159–1167. [2] G.I. Shcherbakova, P.A. Storozhenko, D.V. Sidorov, M.Kh. Blokhina, M.G. Kuznetsova,M.V. Polyakova, A.E. Chernyshev, G.Yu. Yurkov, Inorganic Materials, 2011, 47, 5, 535–543. [3] P.A. Storozhenko, G.I. Shcherbakova, A.M. Tsirlin, A.S. Murkina, M.S. Varfolomeev, M.G. Kuznetsova, M.V. Polyakova, O.P. Trokhachenkova, Inorganic Materials, 2007, 43, 3, 320–328 [4] P. A. Storozhenko and G. I. Shcherbakova, Inorganic Materials, 2011, 47, 2, 167–171. [5] G.I. Shcherbakova, P.A. Storozhenko, N.B. Kutinova, D.V. Sidorov, M.S. Varfolomeev, M.G. Kuznetsova, M.V. Polyakova, A.E. Chernyshev, A.I. Drachev, G.Yu. Yurkov, Inorganic Materials, 2012, 48, 10, 1058–1063. [6] O.V. Popkov, E.A. Potapova, G.Yu. Yurkov, E.A. Ovchenkov, G.I. Shcherbakova, D.V. Zhigalov, Pespektivnye Materialy, 2012, 1, 18-22. Acknowledgements – The work was supported by the Russian Foundation for Basic Research (project 13-0312014) e-mail: a.galina@mail.ru, c. gy_yurkov@mail.ru P82 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF A NEW N,N – BINAPHTYL – 1,4 – DIAZA-1,3 – BUTADIENE AND STUDY OF ITS REDOX REACTIONS. B. G.Shestakov, A.A. Trifonov, G.K. Fukin, A.V. Cherkasov, E.V. Baranov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA N,N – binaphtyl – 1,4 – diaza-1,3 – butadiene (1) was synthesized according to the standard procedure consisting in a condensation reaction between α-naphtylamine and 2,3butanedione in methanol catalyzed by formic acid in 60% yield. N, N – binaphtyl – 1,4 – diaza-1,3 – butadiene is an interesting object due presence of naphthalene and NCCN fragments which can accept up to 6 electrons (Scheme 1). Scheme 1. The reactions of (1) with varying amounts of alkali metals were investigated. The complete dissolution of metals occurred in these reactions. However, regardless the molar ratio of the reactants (1:2, 1:4, 1:6) only dianionic species has been isolated [C10H7NC(CH3)C(CH3)NC10H7]2-M2+(Sol)n (M = Li, Na; Sol = THF, DME). Furthermore, the trials to obtain a monoanionic form of 1 afforded a mixture of dianionic species and neutral 1 (Scheme 2). Scheme 2. At the same time reactions of ytterbocenes ( 5-C5Me5)2Yb(THF)2 and ( 5C9 7)2Yb(THF)2 with 1 proceeds with the one-electron oxidation of the metal atom and lead to the formation of sandwich complexes Yb(III) containing monoanionic diazabutadiene ligand (Scheme 3). Scheme 3. Thus, reactions of N,N – binaphtyl – 1,4 – diaza-1,3 – butadiene with alkali metals in various ratios lead to the formation of dianionic form of diazadiene, while the reactions of ytterbocenes ( 5-C5Me5)2Yb(THF)2 and ( 5-C9 7)2Yb(THF)2 with 1 proceed with the oneelectron oxidation of the metal atom and lead to the formation of a sandwich complex Yb(III) containing monoanion diazabuthadiene ligand. e-mail: trif@iomc.ras.ru P83 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CARBORANE TUNING PHOTOPHYSICAL PROPERTIES OF PHOSPHORESCENT IRIDIUM(III) COMPLEXES C. Shia and H. Yan* a State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, P. R. CHINA Phosphorescent iridium(III) complexes have been intensively studied for more than 10 years because of their remarkable photophysical properties and various optoelectronic applications[1-3]. To date, they have been widely applied in organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, chemosensors, and bioimaging. Considerable efforts have been devoted to synthesis of highly performed neutral and cationic iridium(III) complexes with tuneable and improved phosphorescent properties through the proper choice of the coordinated ligands. m-1 p-1 1 500 550 Wavelength/ nm o-2 m-2 p-2 2 600 500 600 Wavelength / nm o-1 m-1 p-1 1 700 o-2 m-2 p-2 2 Fig. 1 The structures of neutral and cationic iridium(III) complexes containing carboranes and the model complexes 1 and 2 (middle), and PL spectra of neutral complexes for m-1, p-1 and 1(left) and cationic complexes for o-2, m-2, p-2 and 2 (right) in degassed CH2Cl2. We have synthesized both neutral and cationic iridium(III) complexes containing o-, m- and p-carborane in the cyclometalated C^N ligand, named as o-1, m-1 and p-1 for neutral complexes and o-2, m-2 and p-2 for cationic complexes. As a result, o-carborane was observed to quench phosphorescent emission in neutral complexes, but m- and p-carboranes can strongly enhance emission both in solution and solid state. In the case of cationic complexes the three carborane isomers can both increase quantum yields and significantly adjust emission wavethlengths of these complexes. The preliminary results demonstrate that the steric, electronic and structural factors of carboranes can efficiently tune phosphorescent properties of iridium(III) complexes. [1] M. A. Baldo, M. E. Thompson and S. R. Forrest, Nature, 2000, 403, 750. [2] Q. Zhao, F. Y. Li and C. H. Huang, Chem. Soc. Rev., 2010, 39, 3007. [3] Y. You, Y. Han, Y. M. Lee, S. Y. Park, W. Nam and S. J. Lippard, J. Am. Chem. Soc., 2011, 133, 11488. Acknowledgements - National Natural Science Foundation of China (20925104 and 21271102). e-mail: hyan1965@nju.edu.cn P84 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NEW WELL-DEFINED PALLADIUM-BASED CATALYSTS FOR THE AEROBIC OXIDATION OF ALCOHOLS Oleg N. Shishilova, Cristóbal Melerob, Pilar Palmab, Juan Camporab a N.S. Kurnakov Institute of general and inorganic chemistry of Russian Academy of Sciences, 119991, Leninsky pr., 31, Moscow, RUSSIA. b Instituto de Investigaciones Químicas, CSIC – Universidad de Sevilla, 41092, Avda. Américo Vespucio, 49, Sevilla, SPAIN. Oxidation of alcohols is one of the most important synthetic operations both in the organic chemistry laboratory and in the industry. Although classic oxidation reactions can be very efficient and selective, they often involve the use of stoichiometric reagents and halogenated solvents, resulting in the generation of large amounts of waste. The urgent need for more sustainable processes has prompted the development of mild and selective oxidation methods based on the use of green reagents and solvents. In this context, direct use of O2 as an oxidizing reagent is a very desirable feature for modern synthetic methodologies. Therefore, new catalysts for aerobic oxidation of alcohols have received much attention in recent years. Recently we have synthesized well-defined palladium complexes of the type [Pd(N– O)(X)(L)], in which N–O is an anionic chelate, L is a monodentate base and X is a generic anionic ligand, and tested them in catalytic aerobic alcohol oxidation: L Pd Pd L N-O L O O N CO2H N CH2CO2H N CO2H N SO3H L Pd N-O N O L PhCMe2CH 2 O Pd N CH2CMe2Ph N Pd O CH2CMe2Ph N CO2H O We have developed a versatile synthetic methodology that provides access to a wide variety of neophylpalladium complexes containing different combinations of chelating and monodentate ligands. These complexes were found to promote the aerobic oxidation of benzylic, allylic and aliphatic alcohols by oxygen. Under the catalysis conditions, the Pd–C bond undergoes homolysis, giving rise to the actual active species. Neophylpalladium pyridinecarboxylate complexes are modular. Their synthesis is straightforward and can be readily extended to other complexes containing different chelates and monodentate ligands. Since the activity and selectivity of these catalysts are ligandcontrolled, it is foreseen that the catalyst design can be tuned to improve activity, selectivity and resistance to the aggressive oxidation conditions, or to generate desirable properties such as compatibility with water or other environmentally friendly solvents. Another useful property of this system is that the catalysts perform without additives, facilitating product separation and purification. Also we have been able to come to some relevant mechanistic conclusions. Acknowledgements - We are grateful to the Council of the President of the Russian Federation for young scientists for financial support (project 966.2012.3). e-mail: oshishilov@gmail.com, campora@iiq.csic.es. P85 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND STRUCTURE OF MIXED-METAL DICHALCOGEN COMPLEXES I. Skabitskya, E. Romadina and A. Pasynskii a N.S. Kurnakov Institute of general and Inorganic Chemistry of Russian Academy of Sciences, 119991, Leninsky prospekt, 31, Moscow, RUSSIA. Mixed-metal clusters are of interest as precursors to inorganic materials of complex composition and high homogeneity [1,2]. Recently we have shown that reactions of manganese dimers [CpMn(CO)2]2E2 (E = S,Se) bridged by dichalcogen ligand with platinum complex (PPh3)2Pt(C2Ph2) result in substitution of tolane by coordinated dichalcogen giving [CpMn(CO)2]2E2Pt(PPh3)2 clusters. Side-on coordination of dichalcogen bridge to platinum results in the rupture of conjugated-bond system in Mn2E2 fragment, without chalcogen-chalcogen bond breaking, contrary to usual oxidative additions to dichalcogen bonds. Transmetalation reaction of [CpMn(CO)2]3Te2 with (PPh3)2Pt(C2Ph2) leads to formation of analogous tellurium cluster. Mixed-metal manganese-chromium disulfur complex CpMn(CO)2S2[Cr(CO)5]2 could also be transmetalated by zero-valent platinum with selective loss of one chromium fragment. The reaction of new rhenium-chromium Cp’Re(CO)2S2Cr(CO)5 complex with (PPh3)2Pt(C2Ph2) gives analogous product according to IR-spectroscopy. Otherwise reaction of uncoordinated Cp’Re(CO)2S2 with (PPh3)2Pt(C2Ph2) results in formation of sulfide bridged complex via unstable intermediate. Me OC Re CO Me (PPh3)2Pt(C2Ph2) S S OC S Re CO Pt PPh3 Ph3P Thermal decomposition of some mixed-metal clusters was studied by DSC-TGA. [1] A. First, B. Second and C. Third, Abbreviated Journal Name, 2013, 12, 345-350. [1] J. M. Thomas, B. F. G. Johnson, R. Raja et al, Acc.Chem.Res., 2003, 36, 20. [2] C. Femoni, M. C. Iapalucci, F. Kaswalder et al, Coord.Chem.Rev. 2006, 250, 1580. Acknowledgements Acknowledgements: this work was financially supported by RFBR (grant № 12-0333101a) and The Council on Grants of the President of Russian Federation ( -5635.2013.3) e-mail: skabitskiy@gmail.com P86 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ELECTROCHEMICAL TRANSFORMATIONS AND ANTIRADICAL ACTIVITY OF TRIALKYLANTIMONY(V) O-AMIDOPHENOLATES I. Smolyaninova, A. Poddel’skyb, S. Smolyaninovaa, N. Berberovaa a b Astrakhan state technical university, 414056, Tatisheva srt, 16, Astrakhan, RUSSIA G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. The electrochemical properties of a trialkylantimony(V) o-amidophenolates (I-III) were studied by cyclic voltammetry. The complexes are undergone two-stage electrochemical oxidation in anodic area: the first redox transfer has one electron quasireversible manner; the second one is the irreversible process. But But R = - CH3 (I); R = - C2H5 (II); R = - C6H11 (III) But O O -e SbR3 SbR3 Bu +e N t i Pr Pri (AP-H)SbR3 O N t Bu i Pr -e SbR3 Bu Pri [(ISQ)SbR3]+ N t i Pr Pri [(IBQ)SbR3]++ The introduction of donor alkyl groups leads to decreasing redox potential at 0.1 V in comparison with o-amidophenolate of triphenylantimony(V) [1]. However the depletion of reversibility redox process points out unstability of the radical cation forms. In course of the second electrochemical transfer, the formation of unstable dicationic species occurs. The particles undergo fast decomposition accompanying of o-iminobenzoquinone decoordination. Radical scavenging activity of organoantimony(V) complexes (I-III) was considered in assays with DPPH radical and model peroxidation of oleic acid. N Compound EC50, µmol IC50, µmol Inhibiton of oleic acid oxidation, % 92.7 I Me3Sb(AP-H) 18.9±1.2 21.0±0.9 94.4 II Et3Sb(AP-H) 13.7±0.8 19.5±1.2 97.8 III (C6H11)3Sb(AP-H) 17.6±0.6 21.2±0.7 97.5 IV Ph3Sb(AP-H) 9.0±1.3 The values of EC50 (DPPH test) and IC50 (oleic acid peroxidation) for complexes point out that the compounds can act as an efficient antiradical agent. All complexes are displayed inhibition effect on the process of oleic acid oxidation. The compounds (I-III) are played the role of effective LOOH destructors, as triphenylantimony(V) o-amidophenolate (IV) [1]. In conclusion, our results suggest that the combination organometallic fragment containing of antimony with redox-active ligand leads to appear uncommon properties, which are varied from properties the initial trialkylantimony(V) compounds. [1] I. Smolyaninov, A. Poddel’sky, N. Antonova // J. Organometallic Chemistry, 2011, 696, 2611-2620. Acknowledgements - the work was financially supported by Russian Foundation for Basic Research (grants № 11-03-00389-a, 12-03-31026, 13-03-00487). e-mail: ivsmolyaninov@gmail.com, aip@iomc.ras.ru P87 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REDOX-ISOMERIC TRANSFORMATIONS. ELECTRONIC AND LATTICE CONTRIBUTIONS. N. Skorodumovaa, M. Bubnova, A. Arapovaa, N. Smirnovab, A. Bogom’akovc a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. b Chemistry Research Institute of N.I. Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina av. 23/5,Nizhny Novgorod, RUSSIA. Bis-quinonato cobalt complexes are the promising compounds for studding of regularities of redox-isomeric interconversion. It is actual for intelligible synthesis of redox-isomeric compounds with preprogramed properties. Here we report the synthesis and investigation of the family of 1,10-phenathroline bisquinonato cobalt complexes – derivatives of different quinones and phenanthrolines. Recently we have reported synthesis and properties of (1,10-phen)Co(3,6-DBSQ)2 [1]. Using of oquinonato ligand substituted in 4-position by –OMe group (4-OMe-3,6-DBQ) leads to another redox-isomeric compound. In spite of the difference of redox properties of 3,6-DBQ and 4OMe-3,6-DBQ the temperature of redox-isomeric transition is practically the same. It is the consequence of the presence of solvate molecule in the lattice. In the case of quinonato ligands modified by annulated cycles: and in 4,5-position the trigonal-prismatic complexes are formed. No redox-isomeric transformations are observed in these cases. Modification of 1,10-phenathroline ligand also affects the complex properties. Using the 2,9-dimethyl-1,10-phenanthroline slightly distort complex geometry and as the consequence the redox-isomeric transformation is absent. [1] M. Bubnov et al., Russ.Chem.Bull., Int.Ed., 2011, 60, 440-446. Acknowledgements - We are grateful to the RFBR (grants №№ 13-03-12444, 13-03-97082, 13-03-97070), Russian President Grant supporting Scientific Schools (NSh-1113.2012.3) and Fundamental Research Programm of Presidium of RAS (№ 18) for financial support. e-mail: Skorodumova@iomc.ras.ru P88 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia THE EFFECT OF LIGAND FIELD ON LD LISC A. Starikova, V. Minkinb a Southern Scientific Center of Russian Academy of Sciences, 344006, st. Chehova, 41, Rostov on Don, RUSSIA. b Institute of Physical and Organic Chemistry at Southern Federal University, 344090, Stachka Avenue, 194/2, Rostov on Don, RUSSIA. Coordination compounds whose magnetic properties can be controlled by external stimuli (temperature, pressure and irradiation) serve as building blocks for the design of the magnetically responsive molecular switches and magnets [1]. The well-known effects resulting in switching magnetic properties of metal complexes by means of irradiation are LIESST and LD LISC. The latter consists in the change of ligand field caused by lightinduced cis-trans photoisomerization of photoactive fragments which leads to the manifestation of switchable magnetic properties by one of the forms of the complex. LD LISC effect occurs in solution and thin films of Fe(II) and Fe(III) coordination compounds [2] which fact distinguishes it from the strictly cooperative effect of spincrossover. The magnetically bistable systems exhibiting LD-LISC effect are based on various types of ligands. With the purpose of study of the mechanism of LD LISC effect and the influence of photoinduced isomerisation on the change in the strength of the ligand field the experimentally characterized coordination compounds 1-3 have been theoretically explored. High spin and low spin isomers of the complexes involved and the dependence of the magnetic properties on the packing in the crystals have been studied by the use of the density functional theory B3LYP*/6-311++G(d,p) calculations. [1] P. Gütlich, H.A. Goodwin, Spin Crossover in Transition Metal Compounds I–III in Topics in Current Chemistry, Berlin: Springer-Verlag, 2004, vol. 233–235. [2] . Roux, J. Zarembowitch, B. Gallois, T. Granier, R. Claude, Inorg. Chem. 1994, 33, 2273–2279. Acknowledgements - This work has been supported by the Ministry of Education and Science RF (agreement No 14.A18.21.0808) and the Council for Grants of the President of the Russian Federation for Support of Leading Scientific Schools (grant No NSh-927.2012.3). e-mail: andr@ipoc.sfedu.ru P89 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COORDINATION PROPERTIES OF NOVEL HYBRID LIGANDS BASED ON AMINOMETHYLPHOSPHINES I. Strelnika, S. Ignat’eva, A.Balueva, E. Musina, A.Shamsieva, D. Krivolapov, A. Karasik, and O. Sinyashin a A. E. Arbuzov’s Institute of Organic and Physical Chemistry of Kazan Scince Center of Russian Academy of Sciences, 420088, Arbuzov str, 8, Kazan, RUSSIA. Pyridylphosphines are hybrid ligands which are pre-organized for the design of polynuclear complexes. The metal complexes based on Py-P hybrid ligands are excellent catalysts due to lability of metal-N(Py) bonds. In this work we present a synthesis of novel cyclic aminomethylphosphines with 2-(2-pyridyl)ethyl groups on phosphorus atoms and their coordination properties. The 1,5-di(R)-3,7-bis(2-(2-pyridyl)ethyl-1,5-diaza-3,7-diphosphacylcooctanes 1-3 were obtained by Mannich-like condensation of 2-(2-pyridyl)ethylphosphine, formaldehyde and primary amines in good yields (70-90%). The coordination properties of 1-3 are studied toward d8 and d10 metals. Complexes of Ni(II), Pt(II) are potential catalysts and complexes of Cu(I) are able to show luminescence. Ligands 1 and 2 form with Pt(COD)Cl2 in ratio ligand:metal 2:1 desired bis-P,P-chelate complexes 4 and 5, which are similar to ones described earlier [1]. The interaction of 2 with one equiv. Pt(COD)CI2) leads to the formation of the mixture of neutral [( 2-P,P-2)PtCl2] and cationic [( 3- P,P,N-2)PtCl]Cl complexes. After the reaction of 2 with NiCl2 or Ni(CH3CN)6(BF4)2 the corresponding bis-P,N-chelate complexes 6, 7 were isolated. Bis-P,P-chelate complex as a minor product was observed in the reaction mixture during the formation of 6, but after the solvent removal and the washing of crude powder with methanol only one signal of 6 was registered in the NMR 31P spectra. The reactions of 2 and 3 with copper (I) iodide result in binuclear complexes 8 and 9, where ligands show a P,N-chelate and P,P-bridge coordination mode together. Due to the rigid framework of eight-membered heterocycle, Cu-Cu distance (2.6 Å) is less than sum of Van der Waals radii. The coordination of pyridyl with u(I) and short distance between metal cores is the reason of strong luminescence of complexes 8 and 9. [1] A.A. Karasik, R.N. Naumov, A.S Balueva, Heteroatom Chemistry, 2006, 17, 499-513. Acknowledgements – This work was supported by RFBR (No.13-03-00563- , 12-03-97083-r_povolzhie_a), President’s of RF Grant for the support of leading scientific schools (No.NSh-6667.2012.3). e-mail: igorstrelnik@iopc.ru, elli@iopc.ru P90 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND INVESTIGATION ORGANIC SOLID STATE ACTIVE MEDIA T.N. Kopylovaa, E.N. Telminova, T.A. Solodovaa, S.Yu Nikonov a, D.S.Tabakaev, R.M. Gadirova, L.G. Samsonovaa, E.N. Ponyavinaa a Siberian Physical Technical Institute of Tomsk State University, 634050, Novosobornaya sq., 1, Tomsk, RUSSIA The development of new materials for using as active media for tunable lasers, optical sensors, OLEDs, OSLs has been attracting the attention of researchers in the last years. The priority in the branch of synthesis of solid-state active media based on organic compounds belongs to A.Costela [1]. We continue investigations [2-4] in the field of synthesis of solid-state active media for tunable lasers aimed at investigations of solid-state active media lasing in a wide spectral range and development of lasers on their basis. In the present work, results obtained in the field of synthesis of solid-state active media on the modified methylmetacrylate matrices activated by dyes rhodamine 6G, pyrromethene 567 that effectively generate radiation in the visible range of the spectrum are given. The components of hybrid polymer were organic monomers (MMA – methylmetacrylate, HEMA – hydroxy ethyl metacrylate, TEOS - tetraethoxysilane, 8-POSS - polyhedral oligomeric silsesquioxane). Patterns of changing the lasing characteristics depending on composites and excitation conditions are established. It is demonstrated that the solid-state active media with efficiency and lifetime that are not inferiors to solutions can be synthesized on their basis. [1] A. Costela, I. García-Moreno, R. Sastre, Physical Chemistry Chemical Physics, 2003, 5, 4745-4763. [2] T.N. Kopylova, G.V. Mayer et.al.,Quantum Electronics, 2003, 33 (6), 498-502. [3] T.N. Kopylova, G.V. Mayer et.al., Applied Physics B , 2004, 78, 183-187. [4] T.N. Kopylova, S.S. Anufrik et.al., Russian Physics Journal, 2012, 55 (10), 1137-1142. Acknowledgements –This work was supported in part by the Russian Foundation for Basic Research (grants Nos. 10-02-90007-Bel-a and 12-02-00694-a) and by grant of RF President (SS-512.2012.2). e-mail: kopylova@phys.tsu.ru P91 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REACTIONS IN COORDINATION SPHERE OF o-SEMIQUINONATO NICKEL(II) COMPLEXES I. Teplovaa, M. Bubnova, N. Druzhkova, T. Kocherova a G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. High spin molecules are useful for design of molecular magnets – perspective materials for molecular electronics. Redox active ligands – derivatives of structurally hindered o-quinones can be used for synthesis of paramagnetic six-coordinate compounds. Here we report about products of the reaction between bis-o-semiquinonato nickel(II) complex Ni(3,6-DBSQ)2 and sterically hindered diazabutadienes. Square-planar bissemiquinonato nickel complexes are known to be diamagnetic due to their single diradical nature. Addition of N,N’-dialkyl-1,4-diazabutadiens-1,3 to them leads to formation of stable six coordinate products containing high spin nickel(II) coupled ferromagnetically with two semiquinones: (Alkyl-DAB)Ni(3,6-DBSQ)2. Interaction of Ni(3,6-DBSQ)2 with N,N’-bis(2,6-dimethylphenyl)-1,4-diaza-2,3-dimethyl-butadien-1,3 also leads to six coordinate product: (2,6-Me2-phenyl-DAB)Ni(3,6-DBSQ)2. However according to 1H NMR spectrum this product in solution is partly dissociated into corresponding catecholate complex and free quinone. Interaction of the same bis-semiquinonato nickel with more sterically hindered N,N’-bis-(2,6-di-iso-propylphenyl)-1,4-diazabutadien-1,3 results in two different crystalline products which were identified as six coordinate complex: (2,6-i-Pr2-phenyl-DAB)Ni(3,6DBSQ)2 and co-crystallized corresponding nickel catecholate with guest quinone molecule: (2,6-i-Pr2-phenyl-DAB)Ni(3,6-DBCat)+(3,6-DBQ). Further increasing of steric hindrance of diazabutadiene – using of N,N’-bis-(2,6-di-iso-propylphenyl)-1,4-diaza-2,3-dimethylbutadien-1,3 leads to dimeric catecholate product. Hydrolysis allowed to isolate the dimeric diazabutadiene. Acknowledgements: We are grateful to the RFBR (grants №№ 12-03-31348, 12-03-31367), Russian President Grant supporting Scientific Schools (NSh-1113.2012.3) and Fundamental Research Programm of Presidium of RAS (№ 18), FSP “Scientific and scientific-pedagogical cadres of innovation Russia” for 2009-2013 years (Agreement 8465) for financial support. Also thanks to I.D.Grishin for MALDI experiments, A. Bogom’akov for magnetic measurements and structural research group of our Institute. e-mail: teplova@iomc.ras.ru P92 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia LANTHANIDE COMPLEXES FOR CATALYTIC FORMATION OF C-N AND C-P BONDS A.A. Trifonov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Lanthanide complexes proved to be efficient catalysts for a wide range of conversions of unsaturated substrates (polymerization/oligomerization, hydroamination, hydrosilylation, hydroboration etc). Design of new ligand systems suitable for coordination to rare-earth metals and providing control of their reactivity, catalytic activity/selectivity and investigation of the structure-reactivity relationships are in the focus of our studies. The synthesis of alkyl, hydrido and amido lanthanide complexes supported by various N,N-, N,N,N-, N,N,O-, N,N,P(O)-ligands and their catalytic activity in olefin hydroamination, hydrophosphination, aldehyde hydrophosphonylation will be reported. Acknowledgements – This work was supported by RFBR (Grants N 12-03-93109- Ц И ) e-mail: trif@iomc.ras.ru P93 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia REDOX-AMPHOTERIC TIN(IV) COMPLEXES WITH TETRADENTATE LIGANDS O.Yu. Trofimova, A.V. Piskunov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. We have been interested in synthesis of tin complexes containing the tetradentate ligands for physicochemical measurements in order to establish the potential of these ligands to be involved in redox transformations. The redox inactive metals make it possible to observe pure redox behavior of the coordinated ligand which is not complicated with oxidation or reduction of the metallic center. t-Bu t-Bu t-Bu N t-Bu N t-Bu N N O Sn O t-Bu R R N N t-Bu Sn t-Bu R = Me(1), Et(2), t-Bu(3), Ph(4) O t-Bu R O R t-Bu t-Bu t-Bu R = Me(5), Ph(6) O O Sn O O N t-Bu t-Bu N t-Bu t-Bu 7 Cations of complexes 1-7 and anions of complexes 1-6 were generated chemically by the oxidation with AgBF4 (or I2) or reductions with metallic potassium, respectively. The obtained solutions of cations and anions were examined using X-band EPR spectroscopy. The spin distribution in cations and anions of 1 and 5 were investigated with help of DFT calculations. The oxidation of complexes 5 and 6 with p-quinone results in cyclization of tetradentate ligand with formation of a mixed phenolate/phenoxyl radical. Acknowledgements - We are grateful to the FSP ‘‘Scientiﬁc and Scientiﬁc-Pedagogical Cadres of Innovation Russia’’ for 2009–2013 years (GK 8465), Russian President Grants (NSh-1113.2012.3) for financial support of this work. e-mail: olesya@iomc.ras.ru, pial@iomc.ras.ru P94 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia CATALYTIC SYSTEMS BASED ON RUTHENACARBORANES IN THE CONTROLLED SYNTHESIS OF PERSPECTIVE POLYMER MATERIALS E. Turmina, N. Kiseleva, I. Grishin and D. Grishin Lobachevsky State University of Nizhny Novgorod, 603950, Gagarina prosp, 23/5, Nizhny Novgorod , RUSSIA The development of new synthetic ways to the well-defined polymers is one of the most challenging problems of modern polymer chemistry. Atom Transfer Radical Polymerization (ATRP) is one of the remarkable processes by which precise polymer synthesis may be achieved with an efficient use of organometallic catalysts. In this work the activity of paramagnetic ruthenium complexes with C2B9-carborane ligand in ATRP was investigated in the polymerization of methyl methacrylate (MMA), izobornyl metacrilate (IBMA) and tert-butyl metacrylate (TBMA) in the presence amines of different nature. (CH2)4 PPh2 PhP Ru X X=Br, Cl Our experiments have shown that polymerization of all mentioned monomers in the presence of amines and ruthenacarboranes proceeds without spontaneous acceleration up to high degrees of conversion, even at low catalyst concentrations (0.01 mol.%). The polymers formed had narrow molecular weight distribution. The molecular weight of the samples was in a good agreement with theoretically calculated for ATRP process and dependence of molecular weight of the samples on conversion is linear. At the same time no increase of molecular weight of PIBMA samples is observed. The polydispersity indices remain virtually unchanged at a level of 1.5. A successful synthesis of diblock- and threeblock-copolymers using PMMAmacroinitiator, synthesized in the same conditions was done. Formation block-copolymers is confirmed by SEC by the shift of curve of block-copolymer into the area greater molecular weights relative to the original macroinitiator. The glass transitions temperatures of the synthethised samples indicate their block-copolymer nature. It was shown that the polymers formed in the presence of bromine containing catalysts and initiators had lower molecular weights in comparison with their chlorine counterparts. Thus, systems on the basis of ruthenacarboranes in combination with amines in the presence of halogen-containing catalysts are effective in controlled synthesis of macromolecules. Acknowledgements - This work was supported Russian Ministry of Education and Science (“Federal target program of scientific and scientific-pedagogical personnel of innovation of Russia on 2009-2013”) and Grant of President of Russian Federation (MK-391.2013.3) e-mail: turmina@ichem.unn.ru P95 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS OF HOMO- AND BLOCK-COPOLYMERS USING O-IMINOSEMIQUINONE COMPLEXES OF TIN(IV) L. Vaganovaa, I. Meshcheryakovab, M. Chegerevb, A. Piskunovb and D. Grishina a Nizhny Novgorod State University, 603950, Gagarin av, 23/5, Nizhny Novgorod, RUSSIA. b G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Germanium(IV) and tin(IV) catecholate complexes reversibly reacts with radicals and therefore can be used as a chain growth regulator in polymerization of styrene (St) [1]. Products of interaction of tin(IV) catecholates and carbon-centered radicals - corresponding osemiquinone derivatives - have been detected by EPR [1]. The paramagnetic compounds of tin(IV) - imSQSnR2Cl, where R = Cl, Me, Et, But, and Ph and imSQ - anion radical 3,5-di-tert-butyl-N-(2,6-diisopropylphenyl)-aminophenol, also may be used as regulators of radical polymerizations of MMA initiated by AIBN at 70ºC [2]. Complex imSQSnBut2Cl under given conditions acts as iniferter – the initiator and regulator of radical polymerization of MMA at 70-90°C [2]. To assess the ability of initiating and controlling these complexes, as well as to determine the most probable mechanisms of reactions occurring in the system was studied a number of other features of the polymerization of vinyl monomers. It was shown that complex imSQSnBut2Cl can be the effective initiator for the synthesis of poly(meth)acrylates. In the case of St, the introduction of this complex leads to a reduction autopolymerization rate at 70-90ºC. The initiation of polymerization of St by imSQSnBut2Cl was observed only at 110°C. However, the linear increase MW with conversion and low polydispersity of polymers, an example, ~1.6-2.1 for polyBMA and ~ 1.4-1.9 for polySt, is retained. Conversions of acrylates, acrylonitrile (in monomers weight) or vinyl chloride using imSQSnBut2Cl does not exceed ~ 5-10%. Formation of high MW product polymerization of vinyl acetate in the presence of imSQSnBut2Cl in the range of 50-110°C does not fixed. It was found that polymers prepared in the presence of imSQSnBut2Cl at 70-110ºC capable to reinitiation of polymerization various vinyl monomers. PolyMMA prepared in the presence of AIBN and each of the imSQSnR2Cl at 70-90ºC also can act as a macroinitiators. Based on these polymers possible to obtain block-copolymers of polyMMA-b-polySt, polySt-bpolyBMA and polyBMA-b-polyMMA a broad range of compositions. Copolymers of polyMMA-b-polyAN may be synthesized in strongly polar solvents. Thus, complexes of tin(IV) with redox-active o-iminosemiquinone ligand can act as regulators of chain growth in polymerization of various vinyl monomers initiated by AIBN and without it. [1]. Vaganova, L.B., Maleeva, A.V., Piskunov, A.V., and Grishin, D.F., Izv. Akad. Nauk, Ser. Khim., 2011, №8, P.1594–1601. [2]. L.B. Vaganova, A.A. Shchepalov, I.N. Meshcheryakova, M.G. Chegerev, A.V. Piskunov, D.F. Grishin, 2012, Doklady Chemistry, 2012, V. 447, №12, P.286–292. Acknowledgements - This work was supported by the Russian Foundation for Basis Research (project no. 11– 03–00674). e-mail: vaganova@ichem.unn.ru, pial@iomc.ras.ru P96 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND CRYSTAL STRUCTURE CHARACTERIZATION OF METAL COMPLEXES OF ACYCLIC CHEALTING LIGANDS HAVING CARBOXAMIDE FUNCTIONALITY A. Pratibha Kapoora, Gaurav Vermab, C. Sadhika Khullarb, D. Ramesh Kapoorb, and E. Sanjay Mandalb. a b Department of Chemistry, Panjab University, Chandigarh-160014, INDIA Department of Chemical Sciences, IISER Mohali, S.A.S. Nagar, Punjab-140306, INDIA The pyridine monocarboxamides, such as pyridine-3-carboxamide and pyridine-4carboxamide apart from having medicinal importance are also versatile ligands from crystal engineering point of view. These ligands have the structural adaptability to self assemble into 1D, 2D or 3D frameworks either using hydrogen bonding or coordination polymerization or a combination of both. The coordination geometry of metal ion along with the nature of bridging ligand decides the direction of extension of these architectures. In this presentation, we will report the synthesis and structural characterization of MIIX2-N,Ndialkylisonicotinamide (alkyl = iPr and iBu) complexes, M(II) = Zn(II), Cu(II) and Co(II); and X = Cl-,NO3-,OAc-. X-ray crystal structures of some of these complexes are used to demonstrate the formation of coordination polymers. [1] Ajay Pal Singh Pannu, Pratibha Kapoor, Geeta Hundal, Ramesh Kapoor, Martin Martinez-Ripoll, Rayond J. Butcher and Maninder Singh Hundal, Polyhedron, 2011, 30, 1691-1702. Acknowledgements - The X-ray facility at IISER Mohali is gratefully acknowledged. e-mail: gauravv003@gmail.com, pkapoor@pu.ac.in, sanjaymandal@iisermohali.ac.in, sadhika_oct@yahoo.com . Paddle wheel structure hown by [Cu(OCOCH3)2(L’)]2 (L’ = diisobutylisonicotinamide) rkapoor@iisermohali.ac.in, 1D Coordination polymer of [ZnCl2(L)2]n. (L = diisopropylisonicotinamide) P97 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COPPER(I) COMPLEXES WITH 4-(1H-PYRAZOL-1-YL)PYRIMIDINES: SYNTHESIS, STRUCTURES AND LUMINESCENCE K. Vinogradovaa, V. Krivopalovb, E. Nikolaenkovab, D. Naumova, N. Pervukhinaa, V. Plyusninc, A. Kupryakovc, M. Rakhmanovaa, L. Sheludyakovaa, M. Bushueva a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk, 630090, RUSSIA b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Akad. Lavrentiev Ave., Novosibirsk, RUSSIA c Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, 3, Institutskaya str., Novosibirsk, 630090, RUSSIA Synthesis of luminescent metal complexes is an interesting and important field of coordination chemistry. Cu(I) complexes and clusters are currently one of main classes of luminescent metal compounds based on a relatively abundant and non-toxic element showing interesting photophysic properties. Unfortunately Cu(I) complexes usually show weak emissions (quantum yield () < 1 % ) and short lived excited states. The effective Cu(I) emitters are rather scarce. The aim of this study is to synthesize effective Cu(I)-containing emitters. A series of Cu(I) halide complexes, [CuLnX] (n = 1, 2; X = Cl, Br), [CuLnPPh3X] (n = 1, 2; X = Cl, Br, I; n = 3; X = I), [Cu2(Ln)2I2] (n = 1, 2, 3, 4) and [Cu2L4X2] (X = Cl, Br), based on 4-(1H-pyrazol-1-yl)pyrimidines have been synthesized. The pyrazolylpyrimidine ligands differ by a substituent in the C6 position of the pyrimidine ring (Fig. 1). The emissive properties depend on the structure of heteroaromatic ligands and halide ions. All complexes display luminescence in the visible region, the color of the emission changes from yellow-green to red. Halide ions show strong effect on the luminescent properties of the complexes: the emission intensity increases in the order: Cl- < Br- < I-. The complex [Cu2(L3)2I2] has more expanded conjugated π-system of the ligand in comparison with complexes [Cu2(Ln)2I2] (n = 1, 2, 4) and its emission is red-shifted. In the solid state the mononuclear [CuL1PPh3X] complexes demonstrate a 3MLCT luminescence in yellow-red region. The degree of distortion of pseudo-tetrahedral CuN2PX core determined from X-ray single crystal data and the Stokes shift being an indicator of the degree of excited state distortion decrease in the order: [CuL1PPh3Cl] > [CuL1PPh3Br] > [CuL1PPh3I]. The constants of non-radiation decay decrease in the same sequence with synchronous low frequency shift of the bands in IR spectra. The luminescence quantum yield and excited state lifetimes increase in the reverse order: 1 1 1 [CuL PPh3Cl] ( = 1.7%) < [CuL PPh3Br] ( = 6.3%) < [CuL PPh3I] ( = 29.4%). Thus, suppression of vibrational quenching and more symmetrical coordination core lead to improvement of Cu(I) photoluminescence quantum efficiency. Acknowledgements - the work was financially supported by Russian Foundation for Basic Research (Projects 11-03-00268 and 12-03-31266 mol_a). e-mail: kiossarin@mail.ru P98 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia POLYCONDENSATION OF [Mo2S2O2(H2O)X]2+ TO A CYCLIC CLUSTERS IN PRESENCE OF SOME BIBASIC ACIDS D.S. Vostretsova, A.I. Smolentsev, S.N. Konchenko Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090, Acad. Lavrentiev Ave., 3, Novosibirsk, RUSSIA. Polyoxothiometalates – a new branch of sulfur-containing polyoxometalates (POTMs) as a subclass of the polyoxometalate family. The richness and diversity of POTMs open great opportunities and prospects of this field in fundamental and applied aspects. [1] In this work we represent the results of self-condensation of [Mo2S2O2]2+ oxothiocation to cyclic clusters in the presence of amino acids and diphosphonic acids, which are supposed to act as structure templates. In the case of L-aspartic acid, the compound, (NMe4)3[Mo10S10O10(OH)10 (C4H5O4N)H2O]Cl·21,5H2O, was obtained. Five {Mo2S2O2} building blocks are connected through double hydroxo bridges to give Mo10-ring and acid residue is located within molybdenum ring (fig. 1). In the case of 2, 5 – thiophenphenylenediphosphonic acid a supramolecular assembly [N(CH3)4]4[Mo10S10O10(OH)10(H2O)5]Cl2(C4O4H4P2S)·17H2O was obtained, in which Mo10rings and the acid residues form polymeric chains via hydrogen bonds (fig. 2). Mo S P H O C Mo S O N C H Fig. 1 Fig. 2 [1] Lemonnier J.-F., Duval S., Floquet S., Cadot E. Isr. J. Chem., 2011, 51, 290 – 302. Acknowledgements - The authors are grateful to the Russian Foundation for basic research (grants No. 12-0331530, 12-03-31759, 13-01-01088), and Federal target program "Kadry" (Contract No. 8631) for financial support. e-mail: semochka54@gmail.com, konch@niic.nsc.ru P99 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NEW LANTHANIDE BIS(AMIDINATE) AMIDO COMPLEXES AS EFFECTIVE CATALYSTS FOR THE RING-OPENING POLYMERIZATION OF RAC-LACTIDE AND HYDROPHOSPHONYLATION OF ALDEHYDES M.V. Yakovenko, N.Yu. Udilova, A.V. Cherkasov, G. K. Fukin, A. A. Trifonov G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, Nizhny Novgorod, Russia YakovenkoMV@yandex.ru Amido rare-earth complexes supported by N- donor ligands demonstrated catalytic potential in ring-opening polymerization of cyclic esters, olefin hydroamination and hydrophosphination. We attempted synthesis of new amido complex supported by bulky ansa bis(amidinate) ligand system via one-pot reaction of [1,8-C10H6{NC(tBu)N-2,6-Me2C6H3}2]Na2, NdCl3 and LiN(SiMe3)2 (THF, 25°C). However, this procedure led to the heterobimetallic complex, containing two bis(amidinate) ligands [1,8-C10H6{NC(tBu)N-2,6Me2-C6H3}2]Nd[1,8-C10H6{NC(tBu)N-2,6-Me2-C6H3}{NC(tBu)N-Li(DME)-2,6-Me2C6H3}]·Et2O (1). When NaN(SiMe3)2 was used instead of LiN(SiMe3)2 in a one-pot reaction amido complexes [1,8-C10H6{NC(tBu)N-2,6-Me2-C6H3}2]YN(SiMe3)2 (2), [1,8C10H6{NC(tBu)N-2,6-Me2-C6H3}2]NdN(SiMe3)2THF (3), [1,8-C10H6{NC(tBu)N-2,6-Me2C6H3}2]SmN(SiMe3)2THF (4) were successfully isolated in 43-54% yields. The complexes 14 were characterized by elemental, spectroscopic analyses. Structures of the complexes 1, 2 and 3 were determined by X-ray diffraction studies. Amido complexes 2-4 proved to be efficient initiators for the ring-opening polymerization (ROP) of racemic lactide (rac-LA), which allow to obtain polymers with high molecular weights (Mn up to 79780 g·mol-1), and moderate molecular weight distributions (Mw/Mn=1.35-2.12) Effective immortal ROP of rac-LA was feasible by combining complexes 2-4 with 3-5 eguiv. of isopropanol, effording PLAs whith well controlled molecular weights and narrow polydispersities (Mw/Mn = 1.13-1.29). All these lanthanide amido complexes displayed high catalytic activities in hydrophosphonylation of aldehydes. Addition of diethyl phosphite to benzaldehydes bearing in para position various substituents p-RC6H4C(O)H (R = Me, OMe, Cl) afforded the products in quantitaive yields by employing low loadings of the catalysts (1 mol %) at room temperature in a very short time (15 min). When the reaction was carried out with benzaldehyde or aliphatic aldehydes RC(O)H (R = Pen, Bu, Pr, iPr) longer reaction times were required (24 h) to reach 84-93% yields of products. t-Bu t-Bu SiMe 3 SiMe 3 1 2 3 Acknowledgements: This work is supported by the Russian Foundation of Basic Research (Grant Nos. 11-0300555-a). P100 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SPECTROSCOPIC STUDY OF HYDRIDOTRIS(PYRAZOLYL)BORATE RUTHENIUM HYDRIDES INTERACTION WITH ACIDS AND BASES R. R. Zaripova, G. A. Silantyeva, N. V. Belkovaa, L. M. Epsteina, K. Weiszb and E. S. Shubinaa a A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119334, Vavilova str., 28, Moscow, RUSSIA. b Institut für Biochemie, Ernst-Moritz-Arndt-Universität Greifswald, D-17487, FelixHausdorff-Straβe, 4, Greifswald, GERMANY. Proton transfer processes are of fundamental importance in a number of (bio)chemical and catalytic systems. Our recent mechanistic studies of the protonation reaction of half-sandwich diphosphine ruthenium hydride complexes Cp’RuH(dppe) (Cp’ = C5Me5 [1], C5H5 [2], dppe = Ph2P(CH2)2PPh2) showed the dramatic ligand effect on the direction of the process. Continuing this line of investigation we carried out the detailed variable-temperature IR and NMR spectroscopic studies of protonation of the analogous complex supported by hydridotris(pyrazolyl)borate ligand TpRuH(dppe) (1, Figure 1). Figure 1. Complex 1 and its protonation product 2. The interaction of complex 1 with weak proton donors, e.g. trifluoroethanol, was shown to give the dihydrogen bonded complex TpRu(dppe)H···HOR. The thermodynamic parameters of this process were determined from the temperature dependence of the equilibrium constant and the H···H distance was calculated from the T1 relaxation measurements. Dihydrogen complex 2 can be obtained by protonation of 1 with stronger proton donors and is stable toward further structural transformations. The study of hydrogen bonding of 2 with neutral bases is the main task of our work because of its importance in many processes, e.g. dihydrogen activation in the coordination sphere of metals. There is only single published paper really focused on the M( 2-H2)···B hydrogen bonds (B = base) [3]. The first results of the spectroscopic studies of the interaction of 2 with a number of neutral bases of different strength (pyridine, Et3N, Oc3PO, etc.) will be presented and discussed. [1] N. V. Belkova, P. A. Dub, M. Baya, J. Houghton, Inorg. Chim. Acta, 2007, 360, 149. [2] G. A. Silantyev, O. A. Filippov, P. M. Tolstoy, N. V. Belkova, L. M. Epstein, K. Weisz, E. S. Shubina, Inorg. Chem., 2013, 52, 1787. [3] N. K. Szymczak, L. N. Zakharov, D. R. Tyler J. Am. Chem. Soc., 2006, 128, 15830. Acknowledgements – This work was financially supported by the Russian Foundation for Basic Research (projects No. 11-03-01210 and 13-03-00604) and by the German-Russian Interdisciplinary Science Center (GRISC) funded by the German Federal Foreign Office via the German Academic Exchange Service (DAAD) (project No. C-2012a-4). e-mail: zarrman33@gmail.com, nataliabelk@ineos.ac.ru P101 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia ABOUT PREVIOUSLY UNKNOWN FEATURES OF OXIDATION OF FERROCENE AND ITS DERIVATIVES BY HYDROGEN PEROXIDE IN WATER AND IN ORGANIC SOLVENTS V. M. Fomin and K.S. Zaytceva Lobachevskii Nizhny Novgorod State University, 603950, pr. Gagarina, 23, Nizhny Novgorod, Russia When we studying the mechanism of ferrocene oxidation by hydrogen peroxide recorded previously unknown phenomenon consisting in shifting the absorption band max ferricenium cation (a.b.f.c.) to longer wavelengths and it simultaneously broadening the reaction. The amount of displacement Δ max increases with excess concentration H2O2 relative to the concentration of ferrocene and a ratio up to 90 nm or more. A similar pattern changes a.b.f.c. takes place during the oxidation of a number of derivatives of ferrocene (Fc). At comparable concentrations of the metal complex and H2O2 offset a.b.f.c. not observed. The oxidation of ferrocene other peroxides - t-C4H9OOH or (PhCOO)2 changes in the spectrum of the ferricenium cation also not recorded at any ratio of reactant concentrations. It is shown that the basis of the observed phenomenon is the formation of the radical cation of { ferricenium cation + •OH} at the primary interaction of the metal complex with H2O2 and the subsequent reaction between the radicals of the radical pair mechanism for radical substitution, leading to the formation of hydroxy derivatives of ferrocene and their cations. The consistent accumulation of OH-substituents on the metal complexes and related ferricenium cations causes a continuous shift a.b.f.c. at longer wavelengths. Another previously unknown feature ferrocene oxidation is that the resulting ferricenium cations can react with H2O2 to restoring the neutral complex. A prerequisite for this reaction is detected in time division stages formation ferricenium cation (Fc+) and its interaction with the peroxide, which is taken in large excess compared to the original metallocomplexes. Thus, the overall mechanism of the oxidation of ferrocene and its derivatives must include not only the oxidation of ferrocene to ferricenium ions, but the reaction of cations with OH-radicals and hydrogen peroxide. By varying the ratio of the concentrations of H2O2 and ferrocene, you can make the contribution of these reactions to the overall process of oxidation of the metal complex to reduce its minimum and only to the formation of the ferricenium cation Fc+. e-mail: niih325@bk.ru P102 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia COBALT-INDUCED B-H AND C-H ACTIVATION LEADING TO FACILE B-C COUPLING OF CARBORANEDITHIOLATE AND CYCLOPENTADIENYL R. Zhanga, L. Zhu and H. Yan* a State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, P. R. CHINA We report the one-pot reactions of the 16e half-sandwich complex CpCoS2C2B10H10 (1), methyl propiolate and 3e-donor ligands which have led to selective B-functionalization at carborane with cyclopentadienyl as a functional group at ambient temperature in good yields. Metal-promoted activations of both B–H bond at carborane and C–H bond at Cp unit have taken place sequentially in the cooperation of organic ligands. The reaction requires a 3edonor ligand and an activated alkyne, therefore suitable for a broad range of substrates. This investigation provides a simple and efficient synthetic route to B-functionalized carborane derivatives. [1] R. Zhang, L. Zhu, G. F. Liu, H. M. Dai, Z. Z. Lu, J. B. Zhao and H. Yan*, J. Am. Chem. Soc., 2012, 134, 10341. [2] M. Herberhold*, H. Yan, W. Milius and B. Wrackmeyer*, Angew. Chem., Int. Ed., 1999, 38, 3689. Acknowledgements - National Natural Science Foundation of China (20925104). e-mail: hyan1965@nju.edu.cn P103 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia METHODS FOR OBTAINING NEW ACTIVE MAGNETIC MATERIALS BASED ON MWCNT AND TRANSITION METAL COORDINATION COMPOUNDS E. Zharikovaa, L. Ochertyanova, N. Efimov, V. Minin, Zh. Dobrokhotova, M. Kiskin, A. Bogomyakov, V. Imshennik, Y. Maksimov, R. Shub, M. Grishin, A. Ganin, I. Eremenko. a N. S. Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences, 119991, Leninsky prosp, 31, Moscow, RUSSIA. Multi-walled carbon nanotube (MWNT) is used as modifying agents to various types of materials, for example, to increase strength and heat resistance. MWCNT or composites with MWCNT are used as catalysts for chemical reactions, solar components and fuel elements, electronic and optical devices, chemical sensors, and adsorbing materials [1]. The most promising for the application considered modified MWNTs, nanotubes contain various functional groups, nitrogen or oxygen-containing. This fact encourages the development of various methods of functionalization of MWCNTs and metal-organic fragments of molecules in order to increase the reactivity of the nanotubes and the appearance of unusual physical properties that can expect to receive new types of functional materials [2-4]. Creation of systems that combine magnetic ions on the surface or inside of CNT, is a way to get new types of magnetic materials. It has been shown MWNTs modified with organic groups containing pyridine fragments can interact with transition metal compounds (FeCl3·6H2O (including isotope Fe57), Fe2NiO(Piv)6(HPiv)3 (HPiv = HO2CCMe3) and Cu2(Piv)4(HPiv)2) to form new magnetoactive compounds. Detailed information about the study of composition, structure and properties of the newly prepared compounds M@MWCNT will be presented in the report. [1] H. Chu, L. Wei, R. Cui, J. Wang, Y. Li, Coord. Chem. Rev., 2010, 254, 1117. [2] Zhang, Y.; Franklin, N.; Chen, R.; Dai, H. Chem. Phys. Lett. 2000, 331, 35. [3] Kong, J.; Chapline, M.; Dai, H. AdV. Mater. 2001, 13, 1384. [4] Haremza, J.; Hahn, M.; Krauss, T.; Chen, S.; Calcines, J. Nano Lett. 2002, 2, 1253. This study was financially supported by the Council on Grants of the President of the Russian Federation (grants NSh-2357.2012.3) and the Russian Academy of Science and Federation. e-mail: a.EvgeniyaZharikova@yandex.ru, P104 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia NOVEL CHARGE-COMPENSATED NIDO-CARBORANES WITH AMMONIUM SUBSISTUENT. O.B.Zhidkova, S.V.Timofeev, I.B.Sivaev, Z.A.Starikova, V.I.Bregadze A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119334, Moscow, Vavilov str., 28, RUSSIA. Introduction of ammonium substituents which contains functional group into carborane cage provide wide possibilities both for medical and coordination chemistry. Using different amines we synthesized series of new compounds: Charge-compensated products were isolated in moderate to good yield. Structure of carboranes with Me2NCH2Ph, Me2CH2CN and Me2CH2C≡CH moieties were confirmed by Xray diffraction. In the case of N,N-dimethylaminopropanol, unusual minor seven-member cyclic product was isolated and characterized by NMR 11B-11B COSY and single-crystal X-ray diffraction. Terminal Me2N-group of charge-compensated product Me2N(CH2)2NMe2 can be modified by the reaction with alkyl halogenides: 7,8-C2B9H11-9- Thus series of ammonium-based charge-compensated nido-carboranes synthesized. Also possibility of further modification was demonstrated. was Acknowledgements - This work was supported by Russian Foundation for Basic Research (grant 13-03-00581) e-mail: zolga57@mail.ru P105 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia SYNTHESIS AND CHARACTERIZATION OF NOVEL COBALT COMPLEXES CONTAINING 4,5-DISUBSTITUTED O-SEMIQUINONE A. Zolotukhin, M. Bubnov and V. Cherkasov G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. o-Semiquinonic transition metal complexes are the most widely studied objects of research in the field of redox isomerism. Typically, derivatives of sterically hindered 3,5- and 3,6-ditert-butyl-1,2-benzoquinone are used as a redox active ligand. Compounds based on the osemiquinone ligands with free 3,6-positions of the benzene ring are practically unknown. Two novel cobalt complexes based on sterically unhindered 4,5-bis(diphenylmethyl)-1,2benzoquinone were synthesized. Ph Ph Ph Ph Ph Ph O O Ph Ph Ph Ph Co Ph O O Ph Ph Ph O Ph O O Ph Co N O N The obtained compounds were investigated by such methods of analysis as IR- and EPR spectroscopy, variable temperature magnetic susceptibility measurements and elemental analysis. The presence of the intensive band corresponding to vibrations of sesquialteral CO bond in the IR spectra of the obtained compounds indicates the semiquinonic type of ligand coordination. However, there is low intensity of absorption at 4000 cm-1 corresponding to the catechol-semiquinone LLCT band in the spectrum of the complex with dipyridyl. EPR spectrum of the powder of complex with neutral donor ligand has a typical for redox isomeric complexes of cobalt temperature dependence – line broadening simultaneously with decreasing of signal intensity with increasing temperature. EPR spectroscopy data are generally consistent with the results of magnetic measurements. The value of the effective magnetic moment of the complex with dipyridyl uniformly increases with increasing temperature, but even at 370 K the curve of the temperature dependence does not reach a plateau. These data suggest that the heteroligand complex undergoes redox isomeric conversion in a wide temperature range. Acknowledgements. The authors are thankful to RFBR (grants: 13-03-97070, 13-03-12444, 13-03-97082), Russian president grant supporting scientific schools ( Ш-1113.2012.3) and Program of Presidium of RAS №18 for financial support and A. Bogomyakov for magnetic measurements. e-mail: zolotukhin1988@mail.ru P106 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia POLYNUCLEAR COMPLEXES OF Co(II) AND Ni(II) WITH DIMETHYLMALONATE ANIONS, CONTAINING CROWN ETHERS E.N. Zorinaa, N.V. Gogoleva, M.A. Kiskina, A.A. Sidorov a, G.G. Aleksandrov a, A.S. Bogomyakovb, I.L. Eremenkoa a N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, Moscow, 119991, Russian Federation b Institute International tomographic center, Siberian branch of the Russian Academy of Sciences, Institutskaya Str. 3a, 630090, Novosibirsk, Russian Federation The reaction of potassium dimethylmalonate (K2Me2Mal) and cobalt(II) carboxylates (pivalate or acetate) resulted in {[K6Co36(H2O)28(OH)20(HMe2Mal)2(Me2Mal)28]·58H2O} (1) (where Me2Mal2- is the dimethylmalonate dianion) [1]. Same reactions of nickel(II) salts (acetate, pivalate, chloride) result in crystals (according to IR spectra the compound contains 36-nuclear anion {Ni36}) with a high symmetry group, that complicates refinements of crystal structure. An addition of crown ether in reaction mixture would allow binding the part of the potassium atoms to from new surround of 36-nuclear fragment to low symmetry of crystals. The reaction of {MII(Piv)2} (MII = Co, Ni) and K2Me2Mal in the presence of 18-crown-6 in a mixture of ethanol-water (10:1) led compounds {[K8Co36(H2O)20( )20(18-crown6)4(Me2Mal)30]·14H2O} (2) and {[K6Ni36(H2O)16( )20(18-crown6)2(HMe2Mal)2(Me2Mal)28]·17H2O} (3), respectively. The structure of 36-nuclear anion {M36} in 2 and 3 is similar to the anion of 1. Two potassium atoms are located inside anion {M36} for both complexes. Each potassium atom forms ionic bonds with O atoms of malonate anions (Fig. 1). Anions {M36} in 2 and 3 are bound to each other by {K(H2O)x}+ fragments in chain structure. Addition of dibenzo-18-crown-6 instead of 18-crown-6 in reaction mixture {Co(Piv)2}– K2Me2Mal led the formation of complex {[K8Co36(H2O)12( )20(dibenzo-18-crown6)9(Me2Mal)30]·18H2O}. Compound 2 exhibits low magnetic anisotropy and antiferromagnetic interactions between CoII centers. Compound 3 is characterized by ferromagnetic interactions between nickel(II) ions in 36-nuclear fragment. Fig.1 Potassium atoms inside anion {Ni36} and six dimethylmalonate dianions [1] E.N. Zorina, N.V. Zauzolkova, A.A. Sidorov, G.G. Aleksandrov , A.S. Lermontov, M.A. Kiskin, A.S. Bogomyakov , V.S. Mironov, V.M. Novotortsev, I.L. Eremenko, Inorg. Chem. Acta, 2013, 396, 108-118. Acknowledgements - This study was supported by Russian Foundation of Basic Research (11-03-00735, 12-0331151), The Council on Grants of the President of the Russian Federation (NSh-2357.2012.3), the Russian Academy of Sciences. e-mail: kamphor@mail.ru, sidorov@igic.ras.ru P107 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Author Index. A Abakumov G. ..................................................................................................................................Y15, P4, P26, P42, P47, P73 Abramov P. ............................................................................................................................................................................. Y1 Abramova N. ............................................................................................................................................................................ P1 Adonin S. ................................................................................................................................................................................. S1 Afonin M................................................................................................................................................................................Y31 Agafonova K. ......................................................................................................................................................................... P32 Agarwal R. .............................................................................................................................................................................. O1 Ageshina A............................................................................................................................................................................. P62 Akhmadullina N. ...................................................................................................................................................................... P2 Akhmedov V. .......................................................................................................................................................................... O2 Aldoshin S..................................................................................................................................................................... O24, P80 Aleksandrov G. .............................................................................................................................................Y6, Y13, P29, P107 Alferova A................................................................................................................................................................................ P3 Ambrozevich S....................................................................................................................................................................... S19 Andreev M. ............................................................................................................................................................................ P62 Antina E. ........................................................................................................................................................................ P55, P56 Antoshkov A. ......................................................................................................................................................................... P29 Anyushin A. ............................................................................................................................................................................ Y2 Arapova A. ................................................................................................................................................................ O7, P4, P88 Arefiev Ya.............................................................................................................................................................................. P66 Arkhipov D. ........................................................................................................................................................................... P10 Arkhipova D............................................................................................................................................................................ Y3 Arsenyev M...................................................................................................................................................................... P5, P20 Artemov A..............................................................................................................................................................................Y44 Artyushin O...................................................................................................................................................................... P6, P58 Asachenko A. .........................................................................................................................................................................Y28 Avdeeva V.............................................................................................................................................................................. P78 Avrorin V. ................................................................................................................................................................................ P3 Aysin R. .......................................................................................................................................................................... O8, P48 B Babin V. .................................................................................................................................................................................O30 Balashova T.............................................................................................................................................................................. P7 Balueva A............................................................................................................................................................... S10, P61, P90 Baranov E.........................................................................................................................................P8, P12, P46, P72, P77, P83 Barinova Yu. .................................................................................................................................................................... P8, P72 Basalov I. ................................................................................................................................................................................ Y4 Bashirov D. ..................................................................................................................................................................... Y5, Y36 Basova G. ............................................................................................................................................................................... P72 Baten’kin M. .......................................................................................................................................................................... P50 Batyeva E. ................................................................................................................................................................................ P9 Baukov Yu. ............................................................................................................................................................................ P10 Bazhina E. ............................................................................................................................................................................... Y6 Bazyakina N. ................................................................................................................................................................. O29, P11 Begantsova Yu. ............................................................................................................................................................... O3, P12 Belkova N. .......................................................................................................................................................... Y20, P67, P101 Belova A. ...............................................................................................................................................................................O22 Berberova N. ......................................................................................................................................... P13, P39, P66, P73, P87 Białek-Pietras M.....................................................................................................................................................................O28 Bilyachenko A.................................................................................................................................................................. O4, Y9 Birin K. .................................................................................................................................................................................... S6 Biriukova M. ........................................................................................................................................................................... Y7 Blokhina M. ........................................................................................................................................................................... P14 Bochkarev L. ..................................................................................................................................... O5, P8, P12, P72, P76, P77 Bochkarev M.............................................................................................................................................................. S2, P7, P46 Bodensteiner M. .....................................................................................................................................................................Y16 Bogomyakov A. ............................................................................... S18, O6, Y10, Y33, Y38, P23, P29, P74, P88, P104, P107 Boguslavskii E. ....................................................................................................................................................................... O9 Bregadze V................................................................................................................................................. PL1, O28, P30, P105 Brylev K.................................................................................................................................................................................O31 Bubnov M. ..............................................................................................................................O7, P4, P42, P53, P88, P92, P106 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Buchachenko A. ....................................................................................................................................................................... S3 Budnikova Y. ........................................................................................................................................................................... S4 Bukalov S........................................................................................................................................................................ O8, P48 Burdukov A............................................................................................................................................................................. O9 Burlov A................................................................................................................................................................................. P15 Bushuev M. ................................................................................................................................................................... O10, P98 Buyanovskaya A. ................................................................................................................................................................... P30 Buznik B. ................................................................................................................................................................................ Y7 Bylikin S. ............................................................................................................................................................................... P10 C Cador O. ................................................................................................................................................................................. S16 Campora J. ............................................................................................................................................................................. P85 Canac Y..................................................................................................................................................................................Y42 Carlos L.................................................................................................................................................................................. S13 Carpentier J.-F......................................................................................................................................................................... Y4 Chalkov N. .............................................................................................................................................................................. Y8 Chauvin R. .............................................................................................................................................................................Y42 Chechet Yu.............................................................................................................................................................................O33 Chegerev M............................................................................................................................................................ P16, P71, P96 Cherkasov A........................................................................................................................ Y4, Y18, Y32, P17, P46, P83, P100 Cherkasov R...................................................................................................................................................................P18, P19 Cherkasov V.......................................................................................................... O7, Y8, Y15, P39, P42, P43, P53, P73, P106 Chernyavskii A....................................................................................................................................................................... P65 Chervonova U. ....................................................................................................................................................................... P34 Chesnokov S. ................................................................................................................................................................... P5, P20 Chizhevsky I. .........................................................................................................................................................................O16 Chubukaeva D........................................................................................................................................................................ P19 Chulanova E. ..........................................................................................................................................................................Y33 Churakov A. .................................................................................................................................................................. Y43, P60 Cosquer G. ............................................................................................................................................................................. S16 D D’yachihin D..........................................................................................................................................................................O16 Daletsky V..............................................................................................................................................................................O10 Davletshina N......................................................................................................................................................................... P18 Dechert S......................................................................................................................................................................... S5, Y26 Degtyarenko K. ...................................................................................................................................................................... P41 Demeshko S. ................................................................................................................................................................... S5, Y26 Demidov V............................................................................................................................................................................. P21 Denisova V.............................................................................................................................................................................O33 Dobrokhotova Zh. ........................................................................................................................................P23, P24, P29, P104 Dodonov V.............................................................................................................................................................................O29 Dolgushin F............................................................................................................................................................................Y37 Domracheva N. ............................................................................................................................................................. O11, P34 Dorodnisyna A. ...................................................................................................................................................................... P22 Dronova M. .......................................................................................................................................................................O4, Y9 Drozdyuk I. ............................................................................................................................................................................ S18 Druzhkov N............................................................................................................................................................ P26, P39, P92 Duckett S................................................................................................................................................................................Y20 Dudkina Y. ............................................................................................................................................................................... S4 Dyson P. ................................................................................................................................................................................ O17 Dzhevakov P. .........................................................................................................................................................................Y28 E Efimov N.............................................................................................................................................Y10, P23, P24, P29, P104 Egorochkin A. ................................................................................................................................................................ P25, P45 Egorova E............................................................................................................................................................................... P26 Eliseeva S...............................................................................................................................................................................Y40 Eltsov I. ................................................................................................................................................................................... O9 Epstein L. ..................................................................................................................................................................... P67, P101 Eremenko ...............................................................................................................................................................................Y10 Eremenko I................................................................................................................................. S11, Y6, Y13, P29, P104, P107 Eremyashev V. ........................................................................................................................................................................ O8 Ermolaev E.............................................................................................................................................................................Y11 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Ermolaev V. ................................................................................................................................................................... O17, Y3 Ershova I. ....................................................................................................................................................................... P27, P71 Evstifeev I. .............................................................................................................................................................................Y10 Evstigneeva E........................................................................................................................................................................ O12 F Fabbiani F. ............................................................................................................................................................................... S5 Fedin M. ................................................................................................................................................................................. S18 Fedorov A. ................................................................................................................................................................... O13, Y29 Fedushkin I..........................................................................................................................O29, Y24, Y26, Y27, P11, P52, P75 Fekete M. ...............................................................................................................................................................................Y20 Ferreira R. .............................................................................................................................................................................. S13 Fesenko T............................................................................................................................................................................... P61 Filippov O. ...................................................................................................................................S17, Y14, Y20, Y37, P35, P67 Flid V. ................................................................................................................................................................................... O14 Fokin S. .................................................................................................................................................................................. P28 Fomin V. .............................................................................................................................................................................. P102 Fomina I. ................................................................................................................................................................................ P29 Fukin G. ................................................................................................................ Y4, Y18, Y32, P7, P17, P73, P79, P83, P100 Fursova E. ....................................................................................................................................................................... O6, P28 G Gadirov R....................................................................................................................................................................... P41, P91 Ganin A. ............................................................................................................................................................................... P104 Garifzyanov A........................................................................................................................................................................ P18 Garnovskii D. ......................................................................................................................................................................... P15 Gatilov Yu..............................................................................................................................................................................O10 Gehman A. ............................................................................................................................................................................. P29 Gerasimova T. ........................................................................................................................................................................Y12 Gerasimova V......................................................................................................................................................................... P29 Gimadiev T. ........................................................................................................................................................................... P19 Glazun S................................................................................................................................................................................. P30 Goeva L.................................................................................................................................................................................. P78 Gogoleva N. ................................................................................................................................................................ Y13, P107 Golhen S................................................................................................................................................................................. S16 Golovnev N. ........................................................................................................................................................................... P49 Golub I. ......................................................................................................................................................................... S17, Y14 Golubenkova L.......................................................................................................................................................................O34 Golubnichya M.............................................................................................................................................................. Y41, P62 Gorbunova Yu.......................................................................................................................................................................... S6 Gracheva Y. ........................................................................................................................................................................... P13 Gradova M. ............................................................................................................................................................................ P31 Grebneva T............................................................................................................................................................................. P33 Grigoriev A. ...........................................................................................................................................................................Y17 Grigorieva I. ........................................................................................................................................................................... P72 Grishin D...................................................................................................................... O15, O16, P22, P38, P40, P70, P95, P96 Grishin I. ........................................................................................................................................................ O16, P7, P32, P95 Grishin M. ............................................................................................................................................................................ P104 Gritsan N. ...............................................................................................................................................................................Y33 Gruselle M..............................................................................................................................................................................O24 Gruzdev M. ............................................................................................................................................................................ P34 Gryaznova T............................................................................................................................................................................. S4 Guari Y......................................................................................................................................................................... PL2, Y25 Guennic B. ............................................................................................................................................................................. S16 Guseva E. ............................................................................................................................................................................... P35 Gushchin A. ........................................................................................................................................................................... P37 Gutsu E................................................................................................................................................................................... P67 H Hosmane N............................................................................................................................................................................ PL3 I Ignat’eva S. ............................................................................................................................................................................ P90 Ignatyev I. ....................................................................................................................................................................... O20, P3 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Ilichev V........................................................................................................................................................................... P8, P76 Ilicheva A................................................................................................................................................................................. P8 Ilinova A. ...............................................................................................................................................................................O28 Ilyakina E. ..................................................................................................................................................................... Y15, P73 Ilychev V.................................................................................................................................................................................. S2 Ilyukhin A. ............................................................................................................................................................. P23, P24, P29 Imshennik V. ........................................................................................................................................................................ P104 Irtegova I. ...............................................................................................................................................................................Y33 Izmaylov B............................................................................................................................................................................. P36 J Jain V. .............................................................................................................................................................................. S7, P30 Jin G.-X.................................................................................................................................................................................... S8 K Kabachy Y..............................................................................................................................................................................O34 Kalashnikova N...................................................................................................................................................................... P10 Kalistratova O. ....................................................................................................................................................................... P37 Kamalov G. .............................................................................................................................................................................. S9 Kaplunov M. .......................................................................................................................................................................... P41 Kapoor A. ............................................................................................................................................................................... P97 Kapoor D................................................................................................................................................................................ P97 Kaprinina A............................................................................................................................................................................ P38 Karasik A. .............................................................................................................................................................. S10, P61, P90 Kargin Yu................................................................................................................................................................................. P2 Karlov S. ....................................................................................................................................................................... Y43, P60 Kasyanenko N. ....................................................................................................................................................................... P21 Kataeva O...............................................................................................................................................................................Y21 Katsaba A............................................................................................................................................................................... S19 Katsyuba S. .......................................................................................................................................................... O17, Y12, P33 Kaul A....................................................................................................................................................................................Y17 Kaushik S. ............................................................................................................................................................................. O18 Kazak V.................................................................................................................................................................................. P29 Kazakov I. ..............................................................................................................................................................................Y16 Ketkov S................................................................................................................................................................................. P12 Khamaletdinova N.......................................................................................................................................................... P25, P45 Khan A. ................................................................................................................................................................................. O19 Kharchenko A. .......................................................................................................................................................................Y17 Khrizanforov M........................................................................................................................................................................ S4 Khrizanforova V....................................................................................................................................................................... S4 Khullar C................................................................................................................................................................................ P97 Khvoinova N. ......................................................................................................................................................................... P52 Kirik S.................................................................................................................................................................................... P49 Kirilin A. ................................................................................................................................................................................. Y9 Kirkina V................................................................................................................................................................................ P67 Kiseleva N.............................................................................................................................................................................. P95 Kiskin M. ......................................................................................................................................... S11, Y10, Y13, P104, P107 Kissel A..................................................................................................................................................................................Y18 Knyazeva E. ...........................................................................................................................................................................O13 Kocherova T................................................................................................................................................................... P39, P92 Kochetkov K. .........................................................................................................................................................................O23 Kochina T........................................................................................................................................................................ O20, P3 Koldaeva Yu. ......................................................................................................................................................................... P66 Kolker A................................................................................................................................................................................. P34 Kolodiazhnyi O. ..................................................................................................................................................................... P18 Kolodina A............................................................................................................................................................................. P80 Kolotilov S. ................................................................................................................................................................... S11, Y10 Kolyada M.............................................................................................................................................................................. P13 Kolyakina E............................................................................................................................................................................ P40 Konchenko S. ....................................................................................................................... S12, O25, Y5, Y30, Y31, Y36, P99 Kopylova T. ................................................................................................................................................................... P41, P91 Korenev V. .............................................................................................................................................................................Y19 Korlukov A. ............................................................................................................................................................................ O4 Korlyukov A. ......................................................................................................................................................................... P10 Kornev A............................................................................................................................................................................... O21 Korol’kov I.............................................................................................................................................................................O10 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Korolev S. .............................................................................................................................................................................. P53 Koroteev P...................................................................................................................................................................... P23, P24 Korshunova E......................................................................................................................................................................... P15 Koshkin S............................................................................................................................................................................... P18 Kostjuk S................................................................................................................................................................................Y43 Kotova O. ...............................................................................................................................................................................Y40 Kozhanov K. .......................................................................................................................................................................... P42 Kozinets E. .............................................................................................................................................................................Y20 Kozlova S................................................................................................................................................................................. S1 Kramarova E. ......................................................................................................................................................................... P10 Krayushkina A. ......................................................................................................................................................................Y21 Krishtop T. .............................................................................................................................................................................Y34 Krivolapov D.................................................................................................................................................................. P19, P90 Krivopalov V................................................................................................................................................................. O10, P98 Kudinov A..............................................................................................................................................................................O22 Kukhto A................................................................................................................................................................................ P41 Kupryakov A.......................................................................................................................................................................... P98 Kuratieva N. ...........................................................................................................................................................................Y33 Kurnosov N. ...........................................................................................................................................................................Y22 Kuropatov V.................................................................................................................................................................... Y8, P43 Kursheva L............................................................................................................................................................................... P9 Kurskii Yu.............................................................................................................................................................................. P44 Kushwah N............................................................................................................................................................................... S7 Kuzmina N. ...........................................................................................................................................................Y39, Y40, P57 Kuznetsov N........................................................................................................................................................................... P78 Kuznetsova O. ................................................................................................................................................. O6, P25, P28, P45 Kuznetsova Y. ........................................................................................................................................................................ P51 Kuzyaev D.............................................................................................................................................................................. P46 L Larionova J..................................................................................................................................................... PL2, S13, O4, Y25 Laskova J................................................................................................................................................................................O28 Lazarev N............................................................................................................................................................................... P47 Leites L. .......................................................................................................................................................................... O8, P48 Lepnev L. ...............................................................................................................................................................................Y40 Lermontov A. .........................................................................................................................................................................Y13 Leshok D. ............................................................................................................................................................................... P49 Lesnikowski Z........................................................................................................................................................................O28 Levchenkov S......................................................................................................................................................................... P15 Levitsky M. .......................................................................................................................................................................O4, Y9 Levshanov G. ......................................................................................................................................................................... P56 Li Y. .......................................................................................................................................................................................O24 Lider E. ..................................................................................................................................................................................Y23 Litvinov I................................................................................................................................................................................ P19 Lobanov A.............................................................................................................................................................................. P31 Lobanova I. ............................................................................................................................................................................O28 Loginov D. ............................................................................................................................................................................ O22 Lokteva A...................................................................................................................................................................... O33, P50 Long J............................................................................................................................................................. PL2, S13, O4, Y25 Lopatin M......................................................................................................................................................................O33, Y29 Lopatina T. .............................................................................................................................................................................O33 Ludin D. ................................................................................................................................................................................. P51 Luk’yanov A. .................................................................................................................................................................. O7, P53 Lukoyanov A......................................................................................................................................................... Y24, P52, P75 Lyssenko K. ........................................................................................................................................................................... P15 Lytvynenko A................................................................................................................................................................ S11, Y10 Lyubov D. .......................................................................................................................................................................Y4, Y18 M Magdesieva T. ............................................................................................................................................................... O23, P64 Mahrova T..............................................................................................................................................................................Y32 Mainichev D...................................................................................................................................................................... S1, Y2 Makarevich A.........................................................................................................................................................................Y39 Makarova N............................................................................................................................................................................ P80 Maksimov Y......................................................................................................................................................................... P104 Maleeva A. .....................................................................................................................................................................P22, P54 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Malinina E.............................................................................................................................................................................. P78 Mandal E. ............................................................................................................................................................................... P97 Manoury E..............................................................................................................................................................................Y20 Marfin Yu.......................................................................................................................................................................P55, P56 Markina O. .............................................................................................................................................................................Y24 Martynov A. ............................................................................................................................................................................. S6 Martynova I............................................................................................................................................................................ P57 Masoud S................................................................................................................................................................................ P64 Mathur P.................................................................................................................................................................................O32 Matveeva E. .....................................................................................................................................................................P6, P58 Maurin-Pasturel G. .................................................................................................................................................................Y25 Maury O. ................................................................................................................................................................................ S16 Melero C. ............................................................................................................................................................................... P85 Menkova P. ............................................................................................................................................................................ P59 Merkushev D.......................................................................................................................................................................... P56 Meshcheryakova I. ......................................................................................................................................................... P71, P96 Meyer F. .......................................................................................................................................................................... S5, Y26 Mialochkin D. .......................................................................................................................................................................... P3 Mihailov M. ...........................................................................................................................................................................O31 Milaeva E. ..................................................................................................................................................................... PL4, P13 Miluykov V. ................................................................................................................................................................... O17, Y3 Milyukov V. ...........................................................................................................................................................................Y21 Minin V. ............................................................................................................................................................................... P104 Minkin V. .............................................................................................................................................................. Y35, P80, P89 Minkina V. ............................................................................................................................................................................. P15 Minyaev R..............................................................................................................................................................................Y35 Mironov Y..............................................................................................................................................................................Y11 Morozov A. ............................................................................................................................................................................Y26 Morozov O. ............................................................................................................................................................................Y28 Moshkin E. ............................................................................................................................................................................. P60 Moskalev M. ..........................................................................................................................................................................Y27 Movchan T. ............................................................................................................................................................................ P82 Mukhatova E. ......................................................................................................................................................................... P13 Muravyov V. ........................................................................................................................................................................... Y5 Murzin V. ............................................................................................................................................................................... P15 Musina E. ...............................................................................................................................................................S10, P61, P90 Mustafina A.....................................................................................................................................................................Y5, Y36 N Naumov D. ............................................................................................................................................................................. P98 Nechaev M. ............................................................................................................................................................................Y28 Nefedov S........................................................................................................................................................ S9, S14, Y41, P62 Nefedova I..................................................................................................................................................................... Y41, P62 Negrebetsky V........................................................................................................................................................................ P10 Nikitenko N............................................................................................................................................................................ P63 Nikitin O. ............................................................................................................................................................................... P64 Nikitina Z. ..............................................................................................................................................................................O24 Nikolaenkova E............................................................................................................................................................. O10, P98 Nikolaevskii S. ............................................................................................................................................................... P15, P80 Nikonov S. ............................................................................................................................................................................. P91 Novikova M. ..........................................................................................................................................................................O33 Novotortsev V. ...............................................................................................................................................S11, P23, P24, P29 Nyuchev A. ............................................................................................................................................................................Y29 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia O Ochertyanova L.................................................................................................................................................................... P104 Odinets I. ................................................................................................................................................................................. P6 Ogarkov A.............................................................................................................................................................................. P65 Ogienko M. ................................................................................................................................................................... S12, Y30 Okhlobystin A. ....................................................................................................................................................................... P66 Okhlobystina A. ..................................................................................................................................................................... P66 Osipova E............................................................................................................................................................................... P67 Osipova V. ............................................................................................................................................................................. P13 Ouahab L................................................................................................................................................................................ S16 Ovanesyan N. ........................................................................................................................................................................ O24 Ovcharenko V. ............................................................................................................................................... S18, O6, Y38, P28 Ovchinnikova Yu. .................................................................................................................................................................. P40 P Pakhomov G.................................................................................................................................................................... O7, P53 Pakhomova T. ........................................................................................................................................................................ P21 Pal M................................................................................................................................................................................ S7, P30 Palma P. ................................................................................................................................................................................. P85 Panova J. ................................................................................................................................................................................O21 Pasynskii A. .................................................................................................................................................. S15, O32, P68, P86 Pasynsky A.............................................................................................................................................................................Y34 Pavlishchuk V. .............................................................................................................................................................. S11, Y10 Pavlova A...............................................................................................................................................................S15, P68, P69 Pavlovskaya M. ...................................................................................................................................................................... P70 Pervukhina N................................................................................................................................................................... O9, P98 Petrov B. ................................................................................................................................................................................ P47 Petrov P. .................................................................................................................................................................................Y31 Petrova A................................................................................................................................................................................O34 Petrovskii P. ........................................................................................................................................................................... P30 Pischur D................................................................................................................................................................................O10 Piskunov A.................................................................................................................... P16, P22, P27, P38, P54, P71, P94, P96 Platonova E. ........................................................................................................................................................................... P72 Plyusnin V.............................................................................................................................................................................. P98 Pochekutova T........................................................................................................................................................................ P44 Poddel’sky A.................................................................................................................................Y15, P40, P73, P74, P81, P87 Pointillart F. ........................................................................................................................................................................... S16 Poli R. ....................................................................................................................................................................................Y20 Polovkova M. ........................................................................................................................................................................... S6 Polunin R................................................................................................................................................................................ S11 Polushkin A.....................................................................................................................................................................O6, Y38 Ponyavina E. .................................................................................................................................................................. P41, P91 Protasenko N. ...........................................................................................................................................................P4, P73, P74 Pushkarev A. ......................................................................................................................................................................S2, P7 Pushkarevsky N.................................................................................................................................................... S12, O25, Y33 Pyataev A. ..............................................................................................................................................................................O11 Q Qi S. ....................................................................................................................................................................................... P36 R Rakhmanova M. ..................................................................................................................................................................... P98 Rao D. ................................................................................................................................................................................... O26 Razborov D. ........................................................................................................................................................................... P75 Roșca S.-C............................................................................................................................................................................... Y4 Roesky H............................................................................................................................................................................... PL5 Romadina E............................................................................................................................................................................ P86 Romanenko G................................................................................................................................................. S18, O6, Y38, P28 Rozhkov A. ............................................................................................................................................................................ P76 Rubina M................................................................................................................................................................................Y28 Rufanov K. ............................................................................................................................................................................ O27 Rumyantsev E. ............................................................................................................................................................... P55, P56 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia S Safronova A. .......................................................................................................................................................................... P77 Safronova E............................................................................................................................................................................ P78 Sagdeev R. ............................................................................................................................................................................. S18 Sakharov S. ............................................................................................................................................................................ P65 Samoilenkov S. ......................................................................................................................................................................Y17 Samsonov M. ......................................................................................................................................................................... P79 Samsonova L.......................................................................................................................................................................... P91 Sarazin Y................................................................................................................................................................................. Y4 Sayapin Yu............................................................................................................................................................................. P80 Sazonova E.............................................................................................................................................................................Y44 Schlangen M. ........................................................................................................................................................................ PL6 Schmalz H.-G................................................................................................................................................................O13, Y29 Schwarz H. .............................................................................................................................................................................PL6 Seidl M...................................................................................................................................................................................Y16 Selikhov A..............................................................................................................................................................................Y32 Seliukov A.............................................................................................................................................................................. S19 Semenov N....................................................................................................................................................................O25, Y33 Semioshkin A. ....................................................................................................................................................................... O28 Sergeeva N. ............................................................................................................................................................................O30 Shaikh M. ...............................................................................................................................................................................O32 Shamsiev R. ...........................................................................................................................................................................O14 Shamsieva A. ................................................................................................................................................................. P61, P90 Shapovalov S......................................................................................................................................................... S15, Y34, P68 Shatunov V............................................................................................................................................................................. P14 Shavyrin A. ....................................................................................................................................................................P44, P81 Shcherbakova G. ............................................................................................................................................................P14, P82 Shegravin K............................................................................................................................................................................Y29 Shekurov R.............................................................................................................................................................................Y21 Sheludyakova L...................................................................................................................................................................... P98 Shestakov A. .......................................................................................................................................................................... P63 Shestakov B............................................................................................................................................................................ P83 Shi C....................................................................................................................................................................................... P84 Shipov A. ............................................................................................................................................................................... P10 Shishilov O.......................................................................................................................................................................P2, P85 Shpakovsky D. ....................................................................................................................................................................... P13 Shub R.................................................................................................................................................................................. P104 Shubina E. .................................................................................................................... S17, O4, Y9, Y14, Y20, Y37, P67, P101 Shul’pin G. .............................................................................................................................................................................. Y9 Shul’pina L.............................................................................................................................................................................. Y9 Shurygina M........................................................................................................................................................................... P20 Shusunova N. ......................................................................................................................................................................... P20 Shutova O............................................................................................................................................................................... P59 Sidorenkov A. ........................................................................................................................................................................Y34 Sidorov A. .............................................................................................................................................................Y6, Y13, P107 Sidorov D. ...................................................................................................................................................................... P14, P82 Silantyev G........................................................................................................................................................................... P101 Simenel A...............................................................................................................................................................................O30 Sinyashin O. ............................................................................................................................ S10, O17, Y3, Y21, P9, P61, P90 Sitnikov N. .............................................................................................................................................................................O13 Sivaev I. ............................................................................................................................................................................... P105 Skabitsky I..................................................................................................................................................... S15, Y34, P68, P86 Skatova A...................................................................................................................................................................... O29, P11 Skorodumova N. ...............................................................................................................................................O7, P4, P53, P88 Smirnova N. ..................................................................................................................................................................... P4, P88 Smol’yakov A. .......................................................................................................................................................................Y37 Smolentsev A. .......................................................................................................................................................Y11, Y23, P99 Smolyaninov I. .......................................................................................................................................................P39, P73, P87 Smolyaninova S. .................................................................................................................................................................... P87 Snegur L................................................................................................................................................................................ O30 Sokolov F. .............................................................................................................................................................................. P19 Sokolov M....................................................................................................................................................................... S1, O31 Sokolov V. ............................................................................................................................................................................... P1 Solntsev K. ............................................................................................................................................................................. P65 Solodova T. .................................................................................................................................................................... P41, P91 Sorochkina K..........................................................................................................................................................................Y28 Sosnin G.................................................................................................................................................................................Y31 Spiridonova Yu. ..................................................................................................................................................................... P61 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Starikov A. ............................................................................................................................................................................. P89 Starikova A. ...........................................................................................................................................................................Y35 Starikova Z................................................................................................................................................................... P30, P105 Storozhenko P. ....................................................................................................................................................................... P59 Strelnik I.........................................................................................................................................................................P61, P90 Sukhikh T........................................................................................................................................................................Y5, Y36 Sushev V. ...............................................................................................................................................................................O21 Suturina L...............................................................................................................................................................................Y33 Suvorova A. ........................................................................................................................................................................... S18 T Tabakaev D. ........................................................................................................................................................................... P91 Tafeenko V............................................................................................................................................................................. P60 Takazova R. ........................................................................................................................................................................... P30 Tauqeer M. .............................................................................................................................................................................O32 Telminov E.....................................................................................................................................................................P41, P91 Teplova I. ............................................................................................................................................................................... P92 Timofeev S........................................................................................................................................................................... P105 Timoshkin A. .........................................................................................................................................................................Y16 Titov A. ......................................................................................................................................................................... Y37, P35 Titov I.....................................................................................................................................................................................O27 Tkachev V. ............................................................................................................................................................................. P80 Tolstikov S. ................................................................................................................................................................... S18, Y38 Topchiy M..............................................................................................................................................................................Y28 Torubaev Yu. ................................................................................................................................................ S15, O32, P68, P69 Train C. ..................................................................................................................................................................................O24 Travkin V. ....................................................................................................................................................................... O7, P53 Tretyakov E.................................................................................................................................................... S18, O6, Y38, P28 Trifonov A................................................................................................................................... Y4, Y18, Y32, P83, P93, P100 Trofimova O........................................................................................................................................................................... P94 Troitskii B. ............................................................................................................................................................................ O33 Tsivadze A. .............................................................................................................................................................................. S6 Tsymbarenko D............................................................................................................................................................. Y39, P57 Tupaeva I................................................................................................................................................................................ P80 Turmina E. .................................................................................................................................................................... O16, P95 U Udilova N............................................................................................................................................................................. P100 Uraev A. ................................................................................................................................................................................. P15 Usoltsev S. ............................................................................................................................................................................. P55 Utochnikova V. ......................................................................................................................................................................Y40 Uvarova M. ................................................................................................................................................................... Y41, P62 V Vabre B. .................................................................................................................................................................................Y42 Vaganova L. ...........................................................................................................................................................P22, P38, P96 Valeeva M. ............................................................................................................................................................................. P18 Valetsky P. ............................................................................................................................................................................ O34 Varfolomeev M. ..................................................................................................................................................................... P82 Vaschenko A. ......................................................................................................................................................................... S19 Vasilchenko I. ........................................................................................................................................................................ P15 Vasilenko I. ............................................................................................................................................................................Y43 Vasnev V................................................................................................................................................................................ P36 Velder J. .................................................................................................................................................................................O13 Verkhovykh R. ....................................................................................................................................................................... P37 Verkhovykh V........................................................................................................................................................................ P37 Verma G. ................................................................................................................................................................................ P97 Vershinin M. .................................................................................................................................................................. O9, O35 Vinogradov M. .......................................................................................................................................................................O22 Vinogradova K. ...................................................................................................................................................................... P98 Vinogradova S........................................................................................................................................................................O34 Vitukhnovsky A. ........................................................................................................................................................... S19, Y40 Vlasenko V............................................................................................................................................................................. P15 Voitovich Yu..........................................................................................................................................................................O13 Vologzhanina A. ......................................................................................................................................................P6, P58, P78 International conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” International Youth School-Conference on Organometallic and Coordination Chemistry September 1-7, 2013, N. Novgorod, Russia Voloshin Y. ............................................................................................................................................................... O9, P6, P58 Vorobeva V. ...........................................................................................................................................................................O11 Voronkov M. ..........................................................................................................................................................................O20 Vorotyntsev M. ...................................................................................................................................................................... P64 Vostretsova D......................................................................................................................................................................... P99 W Wadawale A. .................................................................................................................................................................... S7, P30 Weisz K................................................................................................................................................................................ P101 Y Yakhvarov D. ......................................................................................................................................................................... P12 Yakimansky A........................................................................................................................................................................ P41 Yakovenko M....................................................................................................................................................................... P100 Yamalieva L. .......................................................................................................................................................................... P19 Yan H. ................................................................................................................................................................. O36, P84, P103 Yan N. ................................................................................................................................................................................... O17 Yanberdina N. .......................................................................................................................................................................... P9 Yaremchuk I........................................................................................................................................................................... P18 Yuan X. ................................................................................................................................................................................. O17 Yunin P. ................................................................................................................................................................................. P53 Yurkov G................................................................................................................................................................. Y7, P14, P82 Z Zaitsev K. ...................................................................................................................................................................... Y43, P60 Zaitsev S................................................................................................................................................................................. P51 Zaitseva G. .................................................................................................................................................................... Y43, P60 Zargarian D. .................................................................................................................................................................. S20, Y42 Zaripov R. ............................................................................................................................................................................ P101 Zarovkina N. ..........................................................................................................................................................................Y44 Zaugolnikova A......................................................................................................................................................................Y13 Zavorotny Y. .......................................................................................................................................................................... P29 Zaytceva K. .......................................................................................................................................................................... P102 Zhang R....................................................................................................................................................................... O36, P103 Zharikova E.......................................................................................................................................................................... P104 Zhidkova O. ......................................................................................................................................................................... P105 Zhigalov D. .................................................................................................................................................................... P14, P82 Zhu L........................................................................................................................................................................... O36, P103 Zibarev A. ..................................................................................................................................................... O25, Y5, Y33, Y36 Zolotukhin A. ................................................................................................................................................................ O7, P106 Zolotukhina E......................................................................................................................................................................... P64 Zorina E....................................................................................................................................................................... Y13, P107 Zubavichus Y. ........................................................................................................................................................................ P15 Zueva E. .................................................................................................................................................................................O11 Zvereva E. ....................................................................................................................................................................... O17, P9

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