Proton-Coupled Electron Transfer

Project Graphic Express Summary Small-molecule mononuclear copper(III) compounds, such as hydroxo, peroxo, and benzoate, which mimic biological molecules/enzymes, have been found to initiate hydrocarbon oxidation by activating X–H bonds (X = C, O). These reactions can occur through hydrogen-atom transfer (HAT) or concerted proton-coupling electron transfer (cPCET). In our research, we utilize theoretical techniques such as the analysis of the total dipole moment vector oriented along the hydrogen donor-acceptor axis and direct visualization of the localized intrinsic bond orbitals as they evolve along the reaction coordinate to distinguish between HAT and cPCET mechanisms.