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Reversible Silylene Insertion Reactions into Si−H and P−H σ‐Bonds at Room Temperature |
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| Authors: | Dr. Ricardo Rodriguez Dr. Yohan Contie Raphael Nougué Dr. Antoine Baceiredo Dr. Nathalie Saffon‐Merceron Dr. Jean‐Marc Sotiropoulos Dr. Tsuyoshi Kato |
| Affiliation: | 1. http://hfa.ups‐tlse.fr;2. Université de Toulouse, UPS, and CNRS, LHFA UMR 5069, Toulouse, France;3. CSIC-Universidad de Zaragoza, Departamento de Qu?mica Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Zaragoza, Spain;4. Université de Toulouse, UPS, and CNRS, ICT FR2599, Toulouse, France;5. UNIV PAU & PAYS ADOUR, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, IPREM, ECP, UMR 5254, Pau, France |
| Abstract: | 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. |
| Keywords: | density functional calculations reactive intermediates silylenes structure elucidation X-ray crystallography |