Mechanistic insights into rhodium- and iridium-mediated alkene oxidation with O2

Abstract

The addition of O2 to a coordinated olefin is an effective strategy for the functionalization of organic molecules. Metal-catalyzed oxidation of olefins can give rise to a whole variety of organic products. However, the mechanistic details on how dioxygen binds to the olefin and forms the C-O bond are still not fully understood. We focused on the oxidation of olefins coordinated to Rh and Ir complexes that are known to promote C-O bond formation.

The computational study has revealed that the three complexes evolve through different reaction pathways, despite the similarities between them. The electronic nature of both the metal and the ligand are crucial in the coordination of O2 and its addition to the C=C bond.