Amine Groups in the Second Sphere of Iron Porphyrins Allow for Higher and Selective 4e - /4H + Oxygen Reduction Rates at Lower Overpotentials.

Iron porphyrins with one or four tertiary amine groups in their second sphere are used to investigate the electrochemical O 2 reduction reaction (ORR) in organic (homogeneous) and aqueous (heterogeneous) conditions. Both of these complexes show selective 4e - /4H + reduction of oxygen to water at rates that are 2-3 orders of magnitude higher than those of iron tetraphenylporphyrin lacking these amines in the second sphere. In organic solvents, these amines get protonated, which leads to the lowering of overpotentials, and the rate of the ORR is enhanced almost 75,000 times relative to rates expected from the established scaling relationship for the ORR by iron porphyrins. In the aqueous medium, the same trend of higher ORR rates at a lower overpotential is observed. In situ resonance Raman data under heterogeneous aqueous conditions show that the presence of one amine group in the second sphere leads to a cleavage of the O-O bond in a Fe III -OOH intermediate as the rate-determining step (rds). The presence of four such amine groups enhances the rate of O-O bond cleavage such that this intermediate is no longer observed during the ORR; rather, the proton-coupled reduction of the Fe III -O 2 - intermediate with a H/D isotope effect of 10.6 is the rds. These data clearly demonstrate changes in the rds of the electrochemical ORR depending on the nature of second-sphere residues and explain their deviation from linear scaling relationships.