Density functional theory (DFT) calculations have been carried out to study the detailed mechanism of Pd-catalyzed reductive elimination in C—H bond halogenation reactions under oxidative conditions. The calculation results show that the C—X (Cl) bond formation tends to occur directly on the bimetallic Pd(III) intermediate, without the involvement of the Pd(IV) species. As the first theoretical study on the energy profile of reductive elimination on Pd(III) intermediates, the current theoretical study shows good agreement with the experimental observations reported by Ritter et al., which indicates the reliability of the computational methods. The current study also provides insights into further studies on Pd-catalyzed C—H activation reactions.

Key words: density functional theory, palladium catalyst, C—H halogenation, reductive elimination