Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten

Tetsuya Fukuda; Hisako Hashimoto; Shigeyoshi Sakaki; Hiromi Tobita

doi:10.1002/anie.201507956

Stabilization of a Silaaldehyde by its η² Coordination to Tungsten

Tetsuya Fukuda, Hisako Hashimoto, Shigeyoshi Sakaki, Hiromi Tobita

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

Abstract

Treatment of pyridine-stabilized silylene complexes [(η⁵-C₅Me₄R)(CO)₂(H)W=SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe₃)₃) with an N-heterocyclic carbene ^MeIⁱPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) caused deprotonation to afford anionic silylene complexes [(η⁵-C₅Me₄R)(CO)₂W=SiH(Tsi)][H^MeIⁱPr] (R=Me (1-Me); R=Et (1-Et)). Subsequent oxidation of 1-Me and 1-Et with pyridine-N-oxide (1 equiv) gave anionic η²-silaaldehydetungsten complexes [(η⁵-C₅Me₄R)(CO)₂W{η²-O=SiH(Tsi)}][H^MeIⁱPr] (R=Me (2-Me); R=Et (2-Et)). The formation of an unprecedented W-Si-O three-membered ring was confirmed by X-ray crystal structure analysis.

Original language	English
Pages (from-to)	188-192
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	1
DOIs	https://doi.org/10.1002/anie.201507956
Publication status	Published - 2016 Jan 4

Keywords

metallacycles
silaaldehydes
silanones
silicon
tungsten

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201507956

Cite this

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title = "Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten",

abstract = "Treatment of pyridine-stabilized silylene complexes [(η5-C5Me4R)(CO)2(H)W=SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N-heterocyclic carbene MeIiPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) caused deprotonation to afford anionic silylene complexes [(η5-C5Me4R)(CO)2W=SiH(Tsi)][HMeIiPr] (R=Me (1-Me); R=Et (1-Et)). Subsequent oxidation of 1-Me and 1-Et with pyridine-N-oxide (1 equiv) gave anionic η2-silaaldehydetungsten complexes [(η5-C5Me4R)(CO)2W{η2-O=SiH(Tsi)}][HMeIiPr] (R=Me (2-Me); R=Et (2-Et)). The formation of an unprecedented W-Si-O three-membered ring was confirmed by X-ray crystal structure analysis.",

keywords = "metallacycles, silaaldehydes, silanones, silicon, tungsten",

author = "Tetsuya Fukuda and Hisako Hashimoto and Shigeyoshi Sakaki and Hiromi Tobita",

year = "2016",

month = jan,

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doi = "10.1002/anie.201507956",

language = "English",

volume = "55",

pages = "188--192",

journal = "Angewandte Chemie - International Edition",

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TY - JOUR

T1 - Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten

AU - Fukuda, Tetsuya

AU - Hashimoto, Hisako

AU - Sakaki, Shigeyoshi

AU - Tobita, Hiromi

PY - 2016/1/4

Y1 - 2016/1/4

N2 - Treatment of pyridine-stabilized silylene complexes [(η5-C5Me4R)(CO)2(H)W=SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N-heterocyclic carbene MeIiPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) caused deprotonation to afford anionic silylene complexes [(η5-C5Me4R)(CO)2W=SiH(Tsi)][HMeIiPr] (R=Me (1-Me); R=Et (1-Et)). Subsequent oxidation of 1-Me and 1-Et with pyridine-N-oxide (1 equiv) gave anionic η2-silaaldehydetungsten complexes [(η5-C5Me4R)(CO)2W{η2-O=SiH(Tsi)}][HMeIiPr] (R=Me (2-Me); R=Et (2-Et)). The formation of an unprecedented W-Si-O three-membered ring was confirmed by X-ray crystal structure analysis.

AB - Treatment of pyridine-stabilized silylene complexes [(η5-C5Me4R)(CO)2(H)W=SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N-heterocyclic carbene MeIiPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) caused deprotonation to afford anionic silylene complexes [(η5-C5Me4R)(CO)2W=SiH(Tsi)][HMeIiPr] (R=Me (1-Me); R=Et (1-Et)). Subsequent oxidation of 1-Me and 1-Et with pyridine-N-oxide (1 equiv) gave anionic η2-silaaldehydetungsten complexes [(η5-C5Me4R)(CO)2W{η2-O=SiH(Tsi)}][HMeIiPr] (R=Me (2-Me); R=Et (2-Et)). The formation of an unprecedented W-Si-O three-membered ring was confirmed by X-ray crystal structure analysis.

KW - metallacycles

KW - silaaldehydes

KW - silanones

KW - silicon

KW - tungsten

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