Abstract
Previously only known as fleeting, transient laboratory curiosities in the 1960s, silylenes (species of the general type: SiIIR′R″ where R′ and R″ are any σ or π-bonded substituents, homo or heteroleptic) are now one of the most rigorously investigated classes of compounds in contemporary chemistry. The breakthroughs came in 1986 when Jutzi and co-workers isolated Cp* 2Si: (Cp* = η5-C5Me5), the first isolable Si(II) compound, and later in 1994 with the discovery of the first N-heterocyclic silylene by West and Denk, heralding the beginning of a bourgeoning era in low-valent silicon chemistry. Since these and other key discoveries, massive advances have been made in understanding and elucidating the nature of these reactive compounds, and their ability, for example, to activate small molecules, or behave as ligands in transition metal complexes which can perform a variety of catalytic or stoichiometric transformations. In this chapter, recent advances in silylene chemistry will be presented, with a particular focus on developments in the last 10 years approximately. A key emphasis will rest on the reactivity of isolable silylenes, including their coordination towards metals, with respect to small molecule bond activation, and potential catalytic transformations. Although metal-coordinated silylene complexes have been shown to be catalytically useful in a variety of transformations, metal-free catalysis with silylenes is still a target.
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Notes
- 1.
Compounds featuring silicon atoms in the oxidation state + II that are strictly two coordinate qualify as silylenes in the formal sense. Compounds bearing silicon atoms in the oxidation state + II with π-donating ligands are perhaps better described as monomeric silicon(II) compounds. Nevertheless, given the influence such compounds have had on the development of silylene chemistry in recent years, for our purposes, we relax this definition and include compounds bearing π-coordinated substituents on silicon(II) and treat them as “silylenes.”
Abbreviations
- Ar:
-
Aryl
- Bu:
-
Butyl
- cod:
-
Cyclooctadiene
- concd:
-
Concentrated
- cot:
-
Cyclooctatetraene
- Cp:
-
Cyclopentadienyld
- Dipp:
-
2,6-Bis-isopropylphenyl
- DMAP:
-
4-(Dimethylamino)pyridine
- DMB:
-
3,4-Dimethoxybenzyl
- DME:
-
1,2-dimethoxyethane
- DMF:
-
Dimethylformamide
- DMPU:
-
1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone
- DMSO:
-
Dimethyl sulfoxide
- EDTA:
-
Ethylenediaminetetraacetic acid
- equiv:
-
Equivalent(s)
- Et:
-
Ethyl
- h:
-
Hour(s)
- i-Pr:
-
Isopropyl
- KHMDS:
-
Potassium hexamethyldisilazide potassium bis(trimethylsilyl)amide
- LDA:
-
Lithium diisopropylamide
- LHMDS:
-
Lithium hexamethyldisilazide lithium bis(trimethylsilyl)amide
- LTMP:
-
Lithium 2,2,6,6-tetramethylpiperidide
- Me:
-
Methyl
- Mes:
-
Mesityl 2,4,6-trimethylphenyl (not methanesulfonyl)
- min:
-
Minute(s)
- mol:
-
Mole(s)
- Ph:
-
Phenyl
- Pr:
-
Propyl
- rt:
-
Room temperature
- s:
-
Second(s)
- t-Bu:
-
tert-butyl
- THF:
-
Tetrahydrofuran
- TMEDA:
-
N,N,N',N'-tetramethyl- 1,2-ethylenediamine
- TMS:
-
Trimethylsilyl
- Tol:
-
4-Methylphenyl
- Trip:
-
2,4,6-Triisopropylphenyl
References
Skell PS, Goldstein EJ (1964) Silacyclopropanes. J Am Chem Soc 86:1442
Denk M, Lennon R, Hayashi R, West R, Belyakov AV, Verne HP, Haaland A, Wagner M, Metzler N (1994) Synthesis and structure of a stable silylene. J Am Chem Soc 116:2691
Driess M, Yao S, Brym M, van Wüllen C, Lentz D (2006) A new type of N-heterocyclic silylene with ambivalent reactivity. J Am Chem Soc 128:9628
So CW, Roesky HW, Magull J, Oswald RB (2006) Synthesis and characterization of [PhC(Nt-Bu)2]SiCl: a stable monomeric chlorosilylene. Angewandte Chemie 118:4052
So CW, Roesky HW, Magull J, Oswald RB (2006) Synthesis and characterization of [PhC(Nt-Bu)2]SiCl: a stable monomeric chlorosilylene. Angew Chem Int Ed 45:3948
Sen SS, Roesky HW, Stern D, Henn J, Stalke D (2010) High yield access to silylene RSiCl (R = PhC(Nt-Bu)2) and its reactivity toward alkyne: synthesis of stable disilacyclobutene. J Am Chem Soc 132:1123
Wang W, Inoue S, Irran E, Driess M (2012) Synthesis and unexpected coordination of a silicon(II)-based SiCSi pincerlike arene to palladium. Angewandte Chemie 124:3751; Angewandte Chemie International Edition 51:3691
Wang W, Inoue S, Yao S, Driess M (2012) An isolable bis-silylene oxide (“Disilylenoxane”) and its metal coordination. J Am Chem Soc 132:15890
Wang W, Inoue S, Enthaler S, Driess M (2012) Bis(silylenyl)- and bis(germylenyl)-substituted ferrocenes: synthesis, structure, and catalytic applications of bidentate silicon(II)–cobalt complexes. Angew Chem Int Ed 51:6167
Kong L, Zhang J, Song H, Cui C (2009) N-aryl substituted heterocyclic silylenes. Dalton Trans 28:5444
Zark P, Schäfer A, Mitra A, Haase D, Saak W, West R, Müller T (2010) Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes. J Organomet Chem 695:398
Sen S, Jana A, Roesky HW, Schulzke C (2009) A remarkable base-stabilized bis(silylene) with a silicon(I)–silicon(I) bond. Angew Chem Int Ed 48:8536–8538
Gau D, Rodriguez R, Kato T, Affon-Merceron CA, Cossίo FP, Baceiredo A (2011) A synthesis of a stable disilyne bisphosphine adduct and its non-metal-mediated CO2 reduction to CO. Angew Chem Int Ed 50:1092
Junold K, Baus JA, Burschka C, Tacke R (2012) Bis[N, N′-diisopropylbenzamidinato(−)]silicon(II): A Silicon(II) compound with both a bidentate and a monodentate amidinato ligand. Angewandte Chemie 124:7126
Ding Y, Roesky HW, Noltemeyer M, Schmidt HG, Power PP (2001) Synthesis and structures of monomeric divalent germanium and tin compounds containing a bulky diketiminato ligand. Organometallics 20:1190
Driess M, Yao S, Brym M, van Wuellen C (2006) Low-valent silicon cations with two-coordinate silicon and aromatic character. Angew Chem Int Ed 45:6730
Wang RH, Su MD (2008) Theoretical investigations of the reactivities of cationic six-membered carbene analogues of group 14 elements. J Phys Chem A 112:7689
Jana A, Schulzke C, Roesky HW (2009) Oxidative addition of ammonia at a silicon(II) center and an unprecedented hydrogenation reaction of compounds with low-valent group 14 elements using ammonia borane. J Am Chem Soc 131:4600
Jana A, Roesky HW, Schulzke C, Samuel PP (2009) Insertion reaction of a silylene into a N − H bond of hydrazine and a [1 + 4] cycloaddition with diphenyl hydrazone. Organometallics 28:6574
Präsang C, Stoelzel M, Inoue S, Meltzer A, Driess M (2010) Metallfreie aktivierung von EH3 (E = P, As) durch ein ylid-artiges silylen und bildung eines donorstabilisierten arsasilens mit einer HSi = AsH-untereinheit. Angewandte Chemie 122:10199
Präsang C, Stoelzel M, Inoue S, Meltzer A, Driess M (2010) Metal-free activation of EH3 (E = P, As) by an ylide-like silylene and formation of a donor-stabilized arsasilene with a HSi–AsH subunit. Angew Chem Int Ed 49:10002
Yao S, van Wüellen C, Sun XY, Driess M (2008) Dichotome reaktivität eines stabilen silylens gegenüber terminalen alkinen: C–H-insertion oder autokatalytische bildung von silacycloprop-3-en. Angewandte Chemie 120:3294
Yao S, van Wüellen C, Sun XY, Driess M (2008) Dichotomic reactivity of a stable silylene toward terminal alkynes: facile C–H bond insertion versus autocatalytic formation of silacycloprop-3-ene. Angew Chem Int Ed 47:3250
Xiong Y, Yao S, Brym M, Driess M (2007) Consecutive insertion of a silylene into the P4 tetrahedron: facile access to strained SiP4 and Si2P4 cage compounds. Angew Chem Int Ed 46:4511
Jana A, Samuel PP, Tavčar G, Roesky HW, Schulzke C (2010) Selective aromatic C − F and C − H bond activation with silylenes of different coordinate silicon. J Am Chem Soc 132:10164
Xiong Y, Yao S, Driess M (2009) Reactivity of a zwitterionic stable silylene toward halosilanes and haloalkanes. Organometallics 28:1927
Xiong Y, Yao S, Driess M (2010) Unusual [3 + 1] cycloaddition of a stable silylene with a 2,3-diazabuta-1,3-diene versus [4 + 1] cycloaddition toward a buta-1,3-diene. Organometallics 29:987–990
Xiong Y, Yao S, Driess M (2009) Versatile reactivity of a zwitterionic isolable silylene toward ketones: silicon-mediated, regio- and stereoselective C–H activation. Chemistry 15:5545
Xiong Y, Yao S, Driess M (2009) An isolable NHC-supported silanone. J Am Chem Soc 131:7562–7563
Xiong Y, Yao S, Driess M (2010) Synthesis and rearrangement of stable NHC → silylene adducts and their unique reactivity towards cyclohexylisocyanide. Chemistry 5:322
Yao S, Xiong Y, Driess M (2010) N-heterocyclic carbene (NHC)-stabilized silanechalcogenones: NHC→Si(R2)E (E = O, S, Se, Te). Chemistry 16:1281
Ghadwal RS, Sen SS, Roesky HW, Granitzka M, Kratzert D, Merkel S, Stalke D (2010) Convenient access to monosilicon epoxides with pentacoordinate silicon. Angew Chem Int Ed 49:3952
Sen SS, Khan S, Nagendran S, Roesky HW (2012) Interconnected bis-silylenes: a new dimension in organosilicon chemistry. Acc Chem Res 45:578
Sen SS, Roesky HW, Meindl K, Stern D, Henn J, Stückl AC, Stalke D (2010) Synthesis, structure, and theoretical investigation of amidinatosupported 1,4-disilabenzene. Chem Commun 46:5873
Sen SS, Tavcar G, Roesky HW, Kratzert D, Hey J, Stalke D (2010) Synthesis of a stable four-membered Si2O2 ring and a dimer with two four-membered Si2O2 rings bridged by two oxygen atoms, with five-coordinate silicon atoms in both ring systems. Organometallics 29:2343
Lickiss PD (1992) Transition metal complexes of silylenes, silenes, disilenes and related species. Chem Soc Rev 21:271
Waterman R, Hayes PG, Tilley TD (2007) Synthetic development and chemical reactivity of transition-metal silylene complexes. Acc Chem Res 40:712
Blom B, Stoelzel M, Driess M (2013) New vistas in N-heterocyclic silylene (NHSi) transition-metal coordination chemistry: syntheses, structures and reactivity towards activation of small molecules. Chemistry 19:1
Blom B, Stoelzel M, Driess M (2013) New vistas in N-heterocyclic silylene (NHSi) transition-metal coordination chemistry: syntheses, structures and reactivity towards activation of small molecules. Chemistry 19:40
Meltzer A, Präsang C, Milsmann C, Driess M (2009) Bemerkenswerte stabilisierung von Ni0(η6-Aren)-komplexen durch einen ylid-artigen silylenliganden. Angewandte Chemie 121:3216
Meltzer A, Präsang C, Milsmann C, Driess M (2009) The striking stabilization of Ni0(η6-Arene) complexes by an ylide-like silylene ligand. Angew Chem Int Ed 48:3170
Meltzer A, Präsang C, Driess M (2009) Diketiminate silicon(II) and related NHSi ligands generated in the coordination sphere of nickel(0). J Am Chem Soc 131:7232
Meltzer A, Inoue S, Präsang C, Driess M (2010) Steering S − H and N − H bond activation by a stable N-heterocyclic silylene: different addition of H2S, NH3, and organoamines on a silicon(II) ligand versus its Si(II) → Ni(CO)3 complex. J Am Chem Soc 132:3038
Stoelzel M, Präsang C, Inoue S, Enthaler S, Driess M (2012) Hydrosilylierung von alkinen mit einem Ni(CO)3-stabilisierten silicium(II)-hydrid. Angewandte Chemie 124:411
Stoelzel M, Präsang C, Inoue S, Enthaler S, Driess M (2012) Hydrosilylation of alkynes by Ni(CO)3-stabilized silicon(II) hydrid. Angew Chem Int Ed 51:399
Fürstner A, Krause H, Lehmann CW (2001) Preparation, structure and catalytic properties of a binuclear Pd(0) complex with bridging silylene ligands. Chem Commun 2001:2372
Zhang M, Liu X, Shi C, Ren C, Ding Y, Roesky HW (2008) The synthesis of (η3-C3H5)Pd{Si[N(tBu)CH]2}Cl and the catalytic property for Heck reaction. Zeitschrift für anorganische und allgemeine Chemie (Journal of Inorganic and General Chemistry) 634:1755
Brück A, Gallego D, Wang W, Irran E, Driess M, Hartwig JF (2012) Forcieren der σ-donorstärke in iridium-pinzettenkomplexen: bis(silylen)- und bis(germylen)-liganden sind stärkere donoren als bis[phosphor(III)]-liganden. Angewandte Chemie 124:11645
Brück A, Gallego D, Wang W, Irran E, Driess M, Hartwig JF (2012) Pushing the σ-donor strength in iridium pincer complexes: bis(silylene) and bis(germylene) ligands are stronger donors than bis(phosphorus(III)) ligands. Angew Chem Int Ed 51:11478
Filippou AC, Chernov O, Schnakenburg G (2009) SiBr2(Idipp): a stable N-heterocyclic carbene adduct of dibromosilylene. Angewandte Chemie 121:5797
Ghadwal RS, Roesky HW, Merkel S, Henn J, Stalke D (2009) Lewis base stabilized dichlorosilylene. Angewandte Chemie 121:5793
Filippou AC, Chernov O, Blom B, Stumpf KW, Schnakenburg G (2010) Stable N-heterocyclic carbene adducts of arylchlorosilylenes and their germanium homologues. Chemistry 16:2866
Simons RS, Haubrich ST, Mork BV, Niemeyer M, Power PP (1998)) The syntheses and characterization of the bulky terphenyl silanes and chlorosilanes 2,6-Mes2C6H3SiCl3, 2,6-Trip2C6H3SiCl3, 2,6-Mes2C6H3SiHCl2, 2,6-Trip2C6H3SiHCl2, 2,6-Mes2C6H3SiH3, 2,6-Trip2C6H3SiH3 and 2,6-Mes2C6H3SiCl2SiCl3. Main Group Chem 2:275
Weidemann N, Schnakenburg G, Filippou AC (2009)) Neuartige silane mit sterisch anspruchsvollen aryl-substituenten. Zeitschrift für anorganische und allgemeine Chemie (Journal of Inorganic and General Chemistry) 635:253
Mork BV, Tilley TD (2003) Multiple bonding between silicon and molybdenum: a transition-metal complex with considerable silylyne character. Angewandte Chemie 115:371
Filippou AC, Portius P, Philippopoulos AI, Rohde H (2003) Dreifachbindung zu zinn: synthese und charakterisierung des stannylidinkomplexes trans-[Cl(PMe3)4W≡Sn–C6H3-2, 6-Mes2]. Angewandte Chemie 115:461
Filippou AC, Portius P, Philippopoulos AI, Rohde H (2003) Triple bonding to tin: synthesis and characterization of the stannylyne complex trans-[Cl(PMe3)4W≡Sn–C6H3-2, 6-Mes2]. Angew Chem Int Ed 42:445
Filippou AC, Philippopoulos AI, Schnakenburg G (2003) Triple bonding to tin: synthesis and characterization of the square-pyramidal stannylyne complex cation [(dppe)2WSn−C6H3-2, 6-Mes2] + (dppe=Ph2PCH2CH2PPh2, Mes=C6H2-2,4,6-Me3). Organometallics 22:3339
Filippou AC, Rohde H, Schnakenburg G (2004) Triple bond to lead: synthesis and characterization of the plumbylidyne complex trans-[Br(PMe3)4MoPbC6H3-2,6-Trip2]. Angewandte Chemie 116:2293
Filippou AC, Weidemann N, Schnakenburg G, Rohde H, Philippopoulos AI (2004) Tungsten–lead triple bonds: syntheses, structures, and coordination chemistry of the plumbylidyne complexes trans-[X(PMe3)4WPb(2,6-Trip2C6H3)]. Angewandte Chemie 116:6676
Filippou AC, Chernov O, Stumpf KW, Schnakenburg G (2010) Metall-silicium-dreifachbindungen: synthese und charakterisierung des silylidin-komplexes [Cp(CO)2Mo ≡ Si-R]. Angewandte Chemie 122:3368
Filippou AC, Chernov O, Stumpf KW, Schnakenburg G (2010) Metal–silicon triple bonds: the molybdenum silylidyne complex [Cp(CO)2Mo ≡ Si-R]. Angew Chem Int Ed 49:3296
Blom B (2011) Reactivity of ylenes at late transition metal centres. Doctoral Dissertation. University of Bonn (Published as a book, Cuvillier Verlag, Göttingen, 2011, ISBN-10: 3869559071)
Filippou AC, Chernov O, Schnakenburg G (2011) Chromium Silicon multiple bonds: the chemistry of terminal N-heterocyclic-carbene-stabilized halosilylidyne ligands. Chemistry 17:13574
Gao Y, Zhang J, Hu H, Cui C (2010) Base-stabilized 1-silacyclopenta-2,4-dienylidenes. Organometallics 29:3063
Kira M, Ishida S, Iwamoto T, Kabuto C (1999) The first isolable dialkylsilylene. J Am Chem Soc 121:9722
Asay M, Inoue S, Driess M (2011) Aromatic ylide-stabilized carbocyclic silylene. Angew Chem Int Ed 50:9589
Abe T, Tanaka R, Ishida S, Kira M, Iwamoto T (2012) New isolable dialkylsilylene and its isolable dimer that equilibrate in solution. J Am Chem Soc 134:20029
See reference 20 in 67
Schleyer PR, Maerker C, Dransfeld A, Jiao H, Hommes NJRE (1996) Nucleus-independent chemical shifts: a simple and efficient aromaticity probe. J Am Chem Soc 118:6317
Chen Z, Wannere CS, Corminboeuf C, Puchta R, PvR S (2005) Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem Rev 105:3842
Kira M, Iwamoto T, Ishida S (2007) A helmeted dialkylsilylene. Bull Chem Soc Jpn 80:258
Iwamoto T, Sato K, Ishida S, Kabuto C, Kira M (2006) Synthesis, properties, and reactions of a series of stable dialkyl-substituted silicon−chalcogen doubly bonded compounds. J Am Chem Soc 128:16914
Ishida S, Iwamoto T, Kira M (2011) Addition of a stable dialkylsilylene to carbon–carbon unsaturated bonds. Heteroatom Chem 22:432
Abe T, Iwamoto T, Kabuto C, Kira M (2006) Synthesis, structure, and bonding of stable dialkylsilaketenimines. J Am Chem Soc 128:4228
Takeda N, Kajiwara T, Suzuki H, Okazaki R, Tokitoh N (2003) Synthesis and properties of the first stable silylene–isocyanide complexes. Chemistry 9:3530
Ishida S, Iwamoto T, Kira M (2010) Reactions of an isolable dialkylsilylene with ketones. Organometallics 29:5526
Watanabe C, Iwamoto T, Kabuto C, Kira M (2008) Fourteen-electron bis(dialkylsilylene)palladium and twelve-electron bis(dialkylsilyl)palladium complexes. Angew Chem Int Ed 47:5386
Watanabe C, Inagawa Y, Iwamoto T, Kira M (2010) Synthesis and structures of (dialkylsilylene)bis(phosphine)-nickel, palladium, and platinum complexes and (η6-arene)(dialkylsilylene)nickel complexes. Dalton Trans 39:9414
Sekiguchi A, Tanaka T, Ichinohe M, Akiyama K, Tero-Kubota S (2003) Bis(tri-tert-butylsilyl)silylene: triplet ground state silylene. J Am Chem Soc 125:4962
Tsutsui S, Sakamoto K, Kira M (1998) Bis(diisopropylamino)silylene and its dimer. J Am Chem Soc 120:9955
West R, Fink MJ, Michl J (1981) Tetramesityldisilene, a stable compound containing a silicon-silicon double bond. Science 214:1343
Ando W, Fujita M, Yoshida H, Sekiguchi A (1988) Stereochemistry of the addition of diarylsilylenes to cis- and trans-2-butenes. J Am Chem Soc 110:3310
Driess M (2012) Main group chemistry: breaking the limits with silylenes. Nat Chem 4:525
Rekken BD, Brown TM, Fettinger JC, Tuononen HM, Power PP (2012) Isolation of a stable, acyclic, two-coordinate silylene. J Am Chem Soc 134:6504
Protchenko AV, Birjkumar K, Dange D, Schwarz AD, Vidovic D, Jones C, Kaltsoyannis N, Mountford P, Aldridge S (2012) A stable two-coordinate acyclic silylene. J Am Chem Soc 134:6500
Green SP, Jones C, Stasch A (2007) Stable magnesium(I) compounds with Mg–Mg bonds. Science 318:1754
Protchenko AV, Schwarz AD, Blake MP, Jones C, Kaltsoyannis N, Mountford P, Aldridge S (2013) A generic one-pot route to acyclic two-coordinate silylenes from silicon(IV) precursors: synthesis and structural characterization of a silylsilylene. Angew Chem Int Ed 52:568
Holthausen MC, Koch W, Apeloig Y (1999) Theory predicts triplet ground-state organic silylenes. J Am Chem Soc 121:2623
Jutzi P, Kanne D, Krüger C (1986) Decamethylsilicocen – synthese und struktur. Angewandte Chemie 98:163
Jutzi P, Kanne D, Krüger C (1986) Decamethylsilicocene – synthesis and structure. Angew Chem Int Ed 25:164
Kühler T, Jutzi P (2003) Decamethylsilicocene: synthesis, structure, bonding and chemistry. Adv Organometallic Chem 49:1
Jutzi P, Mix A, Rummel B, Schoeller WW, Neumann B, Stammler HG (2004) The (Me5C5)Si+ cation: a stable derivative of HSi+. Science 305:849
Douglas AE, Lutz BL (1970) Spectroscopic identification of the SiH + molecule: The A1Π–X1Σ + system. Can J Phys 48:247
Singh PD, Vanlandingham FG (1978) Line positions and oscillator strengths of rotation-vibration bands of possible interstellar SiH and SiH+. Astronomy Astrophys 66:87
Xiong Y, Yao S, Inoue S, Irran E, Driess M (2012) The elusive silyliumylidene [ClSi:]+ and silathionium [ClSiS]+ cations stabilized by bis(Iminophosphorane) chelate ligand. Angew Chem Int Ed 51:10074
Leszczyńska K, Mix A, Berger RJF, Rummel B, Neumann B, Stammler HG, Jutzi P (2011) The pentamethylcyclopentadienylsilicon(II) cation as a catalyst for the specific degradation of oligo(ethyleneglycol) diethers. Angew Chem Int Ed 50:6843
Schiemenz B, Power PP (1996) Synthesis of sterically encumbered terphenyls and characterization of their metal derivatives Et2OLiC6H3-2,6-Trip2 and Me2SCuC6H3-2, 6-Trip2(Trip = 2,4,6-i-Pr3C6H2 −). Organometallics 15:958
Jutzi P, Leszczyńska K, Neumann B, Schoeller WW, Stammler HG (2009) [2,6-(Trip)2H3C6](Cp*)Si, eine stabile monomere arylsilicium(II)- verbindung. Angewandte Chemie 121:2634
Jutzi P, Leszczyńska K, Neumann B, Schoeller WW, Stammler HG (2009) [2,6-(Trip)2H3C6](Cp*)Si: a stable monomeric arylsilicon(II) compound. Angew Chem Int Ed 48:2596
Tamm M, Petrovic D, Randoll S, Beer S, Bannenberg T, Jones PG, Grunenberg J (2007) Structural and theoretical investigation of 2-iminoimidazolines – carbene analogues of iminophosphoranes. Org Biomol Chem 5:523
Beer S, Brandhorst K, Hrib CG, Wu X, Haberlag B, Grunenberg J, Jones PG, Tamm M (2009) Experimental and theoretical investigations of catalytic alkyne cross-metathesis with imidazolin-2-iminato tungsten alkylidyne complexes. Organometallics 28:1534
Inoue S, Leszczyńska K (2012) An acyclic imino-substituted silylene: synthesis, isolation, and its facile conversion into a zwitterionic silaimine. Angew Chem Int Ed 51:8589
Jutzi P, Leszczyńska K, Mix A, Neumann B, Rummel B, Schoeller W, Stammler HG (2010) Synthesis and characterization of the ferrio-substituted silicon(II) compound Me5C5(CO)2FeSiC5Me5. Organometallics 29:4759
Leszczyńska K, Abersfelder K, Mix A, Neumann B, Stammler HG, Cowley MJ, Jutzi P, Scheschkewitz D (2012) Reversible base coordination to a disilene. Angew Chem Int Ed 51:6785
Acknowledgements
We are grateful to the Cluster of Excellence “Unicat” (sponsored by the Deutsche Forschungsgemeinschaft (DFG) and administered by the TU Berlin) and the Normalverfahren of the DFG (DR 17–2) for financial support. We also acknowledge Dr S. Yao and Prof Dr S. Inoue for useful material in the preparation of this chapter. We also thank L. van Hoepen for proofreading the final draft.
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Blom, B., Driess, M. (2013). Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis. In: Scheschkewitz, D. (eds) Functional Molecular Silicon Compounds II. Structure and Bonding, vol 156. Springer, Cham. https://doi.org/10.1007/430_2013_95
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