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Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

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Functional Molecular Silicon Compounds II

Part of the book series: Structure and Bonding ((STRUCTURE,volume 156))

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. 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

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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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  1. Institute of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Sekr. C2, Strasse des 17. Juni, 135, 10623, Berlin, Germany

    Burgert Blom & Matthias Driess

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  1. Burgert Blom
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  2. Matthias Driess
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Correspondence to Matthias Driess .

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  1. Chair of General and Inorganic Chemistry, Saarland University, Saarbrücken, Germany

    David Scheschkewitz

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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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