Reduction of dioxygen to water by a Co(N₂O₂) complex with a 2,2'-bipyridine backbone

We report a Co-based complex for the reduction of O₂ to H₂O utilizing decamethylferrocene as chemical reductant and acetic acid as a proton donor in methanol solution. Despite structural similarities to previously reported Co(N₂O₂) complexes capable of catalytic O₂ reduction, this system shows selectivity for the four-electron/four-proton reduction product, H₂O, instead of the two-electron/two-proton reduction product, H₂O₂. Mechanistic studies show that the overall rate law is analogous to previous examples, suggesting that the key selectivity difference arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(iii)-hydroperoxide, instead of the proximal one. Interestingly, no product selectivity dependence is observed with respect to the presence of pyridine, which is proposed to bind trans to O₂ during catalysis.