Selective Four‐Electron Reduction of Oxygen by a Nonheme Heterobimetallic CuFe Complex

Abstract

We report herein the first nonheme CuFe oxygen reduction catalyst ([Cu^II (bpbp)(μ-OAc)₂ Fe^III ]²⁺ , CuFe-OAc), which serves as a functional model of cytochrome c oxidase and can catalyze oxygen reduction to water with a turnover frequency of 2.4×10³ s^-1 and selectivity of 96.0 % in the presence of Et₃ NH⁺ . This performance significantly outcompetes its homobimetallic analogues (2.7 s^-1 of CuCu-OAc with %H₂ O₂ selectivity of 98.9 %, and inactive of FeFe-OAc) under the same conditions. Structure-activity relationship studies, in combination with density functional theory calculation, show that the CuFe center efficiently mediates O-O bond cleavage via a Cu^II (μ-η¹ : η² -O₂ )Fe^III peroxo intermediate in which the peroxo ligand possesses distinctive coordinating and electronic character. Our work sheds light on the nature of Cu/Fe heterobimetallic cooperation in oxygen reduction catalysis and demonstrates the potential of this synergistic effect in the design of nonheme oxygen reduction catalysts.