Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex

Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex [Cu2L(ii- OH)]3+ (L = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold. We show that the electrochemical reduction of [Cu2L(ii- OH)]3+ follows a proton-coupled electron transfer pathway and requires a larger overpotential due to the presence of the Cu-OH Cu motif. In addition, we provide evidence that metal-metal cooperativity takes place during catalysis that is facilitated by the constraints of the rigid ligand framework, by identification of key intermediates along the catalytic cycle of [Cu2L(ii-OH)]3+. Electrochemical studies show that the mechanisms of the ORR and hydrogen peroxide reduction reaction found for [Cu2L(ii- OH)]3+ differ from the ones found for analogous mononuclear copper catalysts. In addition, the metal-metal cooperativity results in an improved selectivity for the four-electron ORR of more than 70% because reaction intermediates can be stabilized better between both copper centers. Overall, the mechanism of the [Cu2L(ii-OH)]3+-catalyzed ORR in this work contributes to the understanding of how the cooperative function of multiple metals in close proximity can affect ORR activity and selectivity.