Catalytic Four-Electron Reduction of O₂ via Rate-Determining Proton-Coupled Electron Transfer to a Dinuclear Cobalt-μ-1,2-peroxo Complex

Abstract

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.