Oxygen Reduction by Iron Porphyrins with Covalently Attached Pendent Phenol and Quinol

Phenols and quinols participate in both proton transfer and electron transfer processes in nature either in distinct elementary steps or in a concerted fashion. Recent investigations using synthetic heme/Cu models and iron porphyrins have indicated that phenols/quinols can react with both ferric superoxide and ferric peroxide intermediates formed during O₂ reduction through a proton coupled electron transfer (PCET) process as well as via hydrogen atom transfer (HAT). Oxygen reduction by iron porphyrins bearing covalently attached pendant phenol and quinol groups is investigated. The data show that both of these can electrochemically reduce O₂ selectively by 4e^-/4H⁺ to H₂O with very similar rates. However, the mechanism of the reaction, investigated both using heterogeneous electrochemistry and by trapping intermediates in organic solutions, can be either PCET or HAT and is governed by the thermodynamics of these intermediates involved. The results suggest that, while the reduction of the Fe^III-O₂̇^- species to Fe^III-OOH proceeds via PCET when a pendant phenol is present, it follows a HAT pathway with a pendant quinol. In the absence of the hydroxyl group the O₂ reduction proceeds via an electron transfer followed by proton transfer to the Fe^III-O₂̇^- species. The hydrogen bonding from the pendant phenol group to Fe^III-O₂̇^- and Fe^III-OOH species provides a unique advantage to the PCET process by lowering the inner-sphere reorganization energy by limiting the elongation of the O-O bond upon reduction.