Disilicon-Mediated Carbon Monoxide Activation: From a 1,2,3-Trisila- to 1,3-Disilacyclopentadienes with Hypercoordinate λ4Si-λ3C Double Bonds
- PMID: 39305142
- DOI: 10.1002/anie.202414696
Disilicon-Mediated Carbon Monoxide Activation: From a 1,2,3-Trisila- to 1,3-Disilacyclopentadienes with Hypercoordinate λ4Si-λ3C Double Bonds
Abstract
The facile reaction of the SiPh2-bridged bis-silylene (LSi:)2SiPh2 (L=PhC(NBut)2) with diphenylacetylene affords the unprecedented 1,2,3-trisilacyclopentadiene (LSi)2(PhC)2SiPh2 1 with a hypercoordinate λ4Si-λ3Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N2O to form the bicyclic oxygenation product 2 through O-atom insertion in the Si=Si and Si-Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3-disilacyclopentadiene 3, representing the first hypercoordinate example of a cyclosilene with a λ4Si-λ3C double bond. Likewise, reaction of Xyl-NC (Xyl=2,6-dimethylphenyl), an isocyanide isoelectronic with CO, with 1 furnishes the related 1,3-disilacyclopentadiene 4 but with an amidinato silylene pendent attached to the Si=C carbon ring atom.
Keywords: alkyne cycloaddition; disilenes; hypercoordination; silaheterocycles; silylenes.
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
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