Rational Design of Mononuclear Iron Porphyrins for Facile and Selective 4e/4H O Reduction: Activation of O-O Bond by 2nd Sphere Hydrogen Bonding.

Facile and selective 4e/4H electrochemical reduction of O to HO in aqueous medium has been a sought-after goal for several decades. Elegant but synthetically demanding cytochrome c oxidase mimics have demonstrated selective 4e/4H electrochemical O reduction to HO is possible with rate constants as fast as 10 M s under heterogeneous conditions in aqueous media. Over the past few years, in situ mechanistic investigations on iron porphyrin complexes adsorbed on electrodes have revealed that the rate and selectivity of this multielectron and multiproton process is governed by the reactivity of a ferric hydroperoxide intermediate. The barrier of O-O bond cleavage determines the overall rate of O reduction and the site of protonation determines the selectivity. In this report, a series of mononuclear iron porphyrin complexes are rationally designed to achieve efficient O-O bond activation and site-selective proton transfer to effect facile and selective electrochemical reduction of O to water. Indeed, these crystallographically characterized complexes accomplish facile and selective reduction of O with rate constants >10 M s while retaining >95% selectivity when adsorbed on electrode surfaces (EPG) in water. These oxygen reduction reaction rate constants are 2 orders of magnitude faster than all known heme/Cu complexes and these complexes retain >90% selectivity even under rate determining electron transfer conditions that generally can only be achieved by installing additional redox active groups in the catalyst.