Critical Aspects of Heme-Peroxo-Cu Complex Structure and Nature of Proton Source Dictate Metal-O(peroxo) Breakage versus Reductive O-O Cleavage Chemistry.

ABSTRACT: The 4H⁺/4e^- reduction of O₂ to water, a key fuel-cell reaction also carried out in biology by oxidase enzymes, includes the critical O-O bond reductive cleavage step. Mechanistic investigations on active-site model compounds, which are synthesized by rational design to incorporate systematic variations, can focus on and resolve answers to fundamental questions, including protonation and/or H-bonding aspects, which accompany electron transfer. Here, we describe the nature and comparative reactivity of two low-spin heme-peroxo-Cu complexes, LS-4DCHIm, [(DCHIm)F₈Fe^III-(O₂^2-)-Cu^II(DCHIm)₄]⁺, and LS-3DCHIm, [(DCHIm)F₈Fe^III-(O₂^2-)-Cu^II

SUBMITTER: Adam SM 

PROVIDER: S-EPMC5274545 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature