An intramolecular ortho-assisted activation of the silicon-hydrogen bond in arylsilanes: an experimental and theoretical study

Dalton Transactions : an International Journal of Inorganic Chemistry
Krzysztof DurkaSergiusz Luliński

Abstract

An intramolecular activation of the Si-H bond in arylsilanes by selected ortho-assisting functional groups based on boron, carbon and phosphorus was investigated experimentally and by means of theoretical calculations. The major conclusion drawn is that the presence of a negatively charged oxygen atom in the functional group is essential for providing effective chelation to the silicon atom which in turn results in the increased hydridic character of a resulting five-coordinated species. In contrast, an intermolecular attack of hydroxide on the silicon atom in aryldimethylsilane results in the activation of the silicon-aryl bond. This increased reactivity of the Si-H bond in intramolecularly coordinated arylsilanes can be ascribed to a significant trans effect which operates in the preferred configuration. Hydrolytic cleavage of the Si-H bond results in dihydrogen elimination and the formation of various silicon heterocyclic systems such as benzosiloxaboroles, spiro-bis(siloxa)borinate, benzosilalactone and benzophosphoxasilole. In addition, intermolecular reduction of benzaldehydes with ortho-boronated arylsilane was observed whereas compounds bearing other reducible functional groups (COMe, COOEt, CN and NO2) were inert under...Continue Reading

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Citations

Dec 14, 2019·Angewandte Chemie·Robin F WeitkampBerthold Hoge
Dec 10, 2019·Journal of the American Chemical Society·Anthony Julien FernandesYannick Landais

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Methods Mentioned

BETA
NMR
X-ray
column chromatography

Software Mentioned

GAUSSIAN09
SHELXL
M06
SHELXS
CrysAlisPro
97

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