Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst

We investigate the mechanism of water oxidation catalyzed by the CuII(pyalk)2 complex, combining density functional theory with experimental measurements of turnover frequencies, UV–visible spectra, H/D kinetic isotope effects (KIEs), electrochemical analysis, and synthesis of a derivative complex. We find that only in the cis form does CuII(pyalk)2 convert water to dioxygen. In a series of alternating chemical and electrochemical steps, the catalyst is activated to form a metal oxyl radical species that undergoes a water-nucleophilic attack defining the rate-limiting step of the reaction. The experimental H/D KIE (3.4) is in agreement with the calculated value (3.7), shown to be determined by deprotonation of the substrate nucleophile upon O–O bond formation. The reported mechanistic findings are particularly valuable for rational design of complexes inspired by CuII(pyalk)2.