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.
A phosphine-stabilized silacyclopropyl cation 2 has been synthesized and fully characterized. Of particular interest, 2 reversibly isomerizes into the corresponding seven-membered cyclic (alkyl)-(amino)silylene 3 at room temperature via a formal migratory ethylene insertion into the SiÀ P bond. Although silylene 3 has not been spectroscopically detected, its transient formation has been evidenced by the isolation of the corresponding disilene dimer 5 as well as by trapping reactions.
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