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 hydro- and chloro-silylenes (2 a,b) undergo an unique dimerization via silylene insertion into SiX σ-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.