Stereoelectronic Substituent Effects on Silylene Insertion into the Si−Cl Bond

Density functional theory calculations for the insertions of Me₂Si: into Si−Cl bonds of various chlorosilanes (YR₂SiCl) revealed hitherto unnoticed remarkable stereoelectronic substituent effects on the transition state (TS) energies, suggesting the importance of the interaction between the silylene lone-pair orbital and the σ*(Si−Y) orbital at the TS.