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

Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E-H sigma-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.