Molecular Mechanism of the Mononuclear Copper Complex-Catalyzed Water Oxidation from Cluster-Continuum Model...

Cluster-continuum model calculations were conducted to decipher the mechanism of water oxidation catalyzed by a mononuclear copper complex. Among various O-O bond formation mechanisms investigated in this study, the most favorable pathway involved the nucleophilic attack of OH^- onto the ^.+ L-Cu^II -OH^- intermediate. During such process, the initial binding of OH^- to the proximity of ^.+ L-Cu^II -OH^- would result in the spontaneous oxidation of OH^- , leading to OH⋅ radical and Cu^II -OH^- species. The further O-O coupling between OH⋅ radical and Cu^II -OH^- was associated with a barrier of 14.8 kcal mol^-1 , leading to the formation of H₂ O₂ intermediate. Notably, the formation of "Cu^III -O^.- " species, a widely proposed active species for O-O bond formation, was found to be thermodynamically unfavorable and could be bypassed during the catalytic reactions. On the basis the present calculations, a catalytic cycle of the mononuclear copper complex-catalyzed water oxidation was proposed.