Reversible Dimerization of Phosphine-Stabilized Silylenes by Silylene Insertion into SiII-H and SiII-Cl σ-Bonds at Room Temperature

Contrary to the classical silylene dimerization leading to a disilene structure, phosphine stabilized hydroand chloro-silylenes (2a,b) undergo an unique dimerization via silylene insertion into Si-X sigma-bonds (X=H, Cl), which is reversible at room temperature. DFT calculations indicate that the insertion reaction proceeds in one step in a concerted manner.