Metal Silylenes Generated by Double Silicon–Hydrogen Activation: Key Intermediates in the Rhodium‐Catalyzed Hydrosilylation of Ketones

Abstract

Rhodium silylenes, which are generated by double Si-H activation at the metal, are involved in a low-activation-barrier mechanism of the hydrosilylation of ketones with R(2)SiH(2). A DFT-based study of reaction mechanisms accounts for the experimental observations, notably the rate enhancement for R(2)SiH(2) over R(3)SiH and an inverse kinetic isotope effect.