Oxidative addition of methane and benzene C–H bonds to rhodium center: A DFT study

Abstract

A density functional theory study on mechanisms of the oxidative addition of methane and benzene C–H bonds to the rhodium center containing Cp and PMe 3 ligands has been performed. Our calculated results confirm that the C–H bond cleavage from a sigma complex to a hydride alkyl complex is the rate-determining step. Compared with the case of methane C–H bond, the oxidative addition of benzene C–H bond is more favorable kinetically and thermodynamically. Stronger backdonation from metal center to the σ ∗ antibonding orbital of benzene C–H bond is responsible for the observations.