Reversible Silylene Insertion Reactions into Si−H and P−H σ-Bonds at Room Temperature

R. Rodriguez , Y. Contie , R. Nougué , A. Baceiredo (1) , N. Saffon-Merceron (2) , Jean-Marc Sotiropoulos (3) , T. Kato (4)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 ICT - Institut de Chimie de Toulouse
3 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
4 Department of Brain Sciences and Molecular Imaging

Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E−H σ-bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Mots clés: Crystallography; density functional calculations; Density functional theory; Insertion reactions; Mild reaction conditions; Oxidative additions; Phosphorus compounds; Reactive intermediate; reactive intermediates; Reductive elimination; Silanes; Silicon centers; silylenes; structure elucidation; X ray crystallography; X-ray crystallography

Domaines: Chimie

R. Rodriguez, Y. Contie, R. Nougué, A. Baceiredo, N. Saffon-Merceron, et al.. Reversible Silylene Insertion Reactions into Si−H and P−H σ-Bonds at Room Temperature. Angewandte Chemie International Edition, 2016, 55 (46), pp.14355--14358. ⟨10.1002/anie.201606728⟩. ⟨hal-01495767⟩