Oxygen Reduction Assisted by the Concert of Redox Activity and Proton Relay in a Cu(II) Complex

A copper complex, [Cu(dpaq)](ClO4) (1), of a monoanionic pentadentate amidate ligand (dpaq) has been isolated and characterized to study its efficacy toward electrocatalytic reduction of oxygen in neutral aqueous medium. The Cu(II) mononuclear complex, poised in a distorted trigonal bipyramidal structure, reduces oxygen at an onset potential of 0.50 V vs RHE. Kinetics study by hydrodynamic voltammetry and chronoamperometry suggests a stepwise mechanism for sequential reduction of O-2 to H2O2 to H2O at a single-site Cu-catalyst. The foot-of-the-wave analysis records a turnover frequency of 5.65 x 10(2) s(-1). At pH 7.0, complex 1 undergoes a quasi-reversible mixed metal-ligand-based reduction and triggers the reduction of dioxygen to water. Electrochemical studies in tandem with quantum chemical investigation, conducted at different redox states, portray the active participation of ligand in completing the process of proton-coupled electron transfer internally. The protonated carboxamido moiety acts as a proton relay, while the quinoline-based orbital supplies the necessary redox equivalent for the conversion of complex 1 to Cu(II)-hydroperoxo species. Thus, a suitable combination of redox non-innocence and proton shuttling functionality in the ligand makes it an effective electron-proton-transfer mediator and subsequently assists the process of oxygen reduction.