Brønsted Acid Scaling Relationships Enable Control over Product Selectivity from O₂ Reduction with a Mononuclear Cobalt Porphyrin Catalyst

The selective reduction of O₂, typically with the goal of forming H₂O, represents a long-standing challenge in the field of catalysis. Macrocyclic transition-metal complexes, and cobalt porphyrins in particular, have been the focus of extensive study as catalysts for this reaction. Here, we show that the mononuclear Co-tetraarylporphyrin complex, Co(por^OMe) (por^OMe = meso-tetra(4-methoxyphenyl)porphyrin), catalyzes either 2e^-/2H⁺ or 4e^-/4H⁺ reduction of O₂ with high selectivity simply by changing the identity of the Brønsted acid in dimethylformamide (DMF). The thermodynamic potentials for O₂ reduction to H₂O₂ or H₂O in DMF are determined and exhibit a Nernstian dependence on the acid pK_a, while the Co^III/II redox potential is independent of the acid pK_a. The reaction product, H₂O or H₂O₂, is defined by the relationship between the thermodynamic potential for O₂ reduction to H₂O₂ and the Co^III/II redox potential: selective H₂O₂ formation is observed when the Co^III/II potential is below the O₂/H₂O₂ potential, while H₂O formation is observed when the Co^III/II potential is above the O₂/H₂O₂ potential. Mechanistic studies reveal that the reactions generating H₂O₂ and H₂O exhibit different rate laws and catalyst resting states, and these differences are manifested as different slopes in linear free energy correlations between the log(rate) versus pK_a and log(rate) versus effective overpotential for the reactions. This work shows how scaling relationships may be used to control product selectivity, and it provides a mechanistic basis for the pursuit of molecular catalysts that achieve low overpotential reduction of O₂ to H₂O.