Kinetic and Mechanistic Characterization of Low-Overpotential, H2O2‑Selective Reduction of O2 Catalyzed by N2O2‑Ligated Cobalt Complexes

A soluble, bis-ketiminate-ligated Co complex [Co­(N2O2)] was recently shown to catalyze selective reduction of O2 to H2O2 with an overpotential as low as 90 mV. Here we report experimental and computational mechanistic studies of the Co­(N2O2)-catalyzed O2 reduction reaction (ORR) with deca­methyl­ferrocene (Fc*) as the reductant in the presence of AcOH in MeOH. Analysis of the Co/O2 binding stoichiometry and kinetic studies support an O2 reduction pathway involving a mononuclear cobalt species. The catalytic rate exhibits a first-order kinetic dependence on [Co­(N2O2)] and [AcOH], but no dependence on [Fc*] or [O2]. Differential pulse voltammetry and computational studies support CoIII-hydroperoxide as the catalyst resting state and protonation of this species as the rate-limiting step of the catalytic reaction. These results contrast previous mechanisms proposed for other Co-catalyzed ORR systems, which commonly feature rate-limiting protonation of a CoIII-superoxide adduct earlier in the catalytic cycle. Computational studies show that protonation is strongly favored at the proximal oxygen of the CoIII(OOH) species, accounting for the high selectivity for formation of hydrogen peroxide. Further analysis shows that a weak dependence of the ORR rate on the pK a values of the protonated CoIII(OOH) species across a series of Co­(N2O2) catalysts provides a rationale for the unusually low overpotential observed for O2 reduction to H2O2.