Phenol-Induced O-O Bond Cleavage in a Low-Spin Heme-Peroxo-Copper Complex: Implications for O2 Reduction in Heme-Copper Oxidases

Journal of the American Chemical Society
Andrew W SchaeferEdward I Solomon

Abstract

This study evaluates the reaction of a biomimetic heme-peroxo-copper complex, {[(DCHIm)(F8)FeIII]-(O22-)-[CuII(AN)]}+ (1), with a phenolic substrate, involving a net H-atom abstraction to cleave the bridging peroxo O-O bond that produces FeIV═O, CuII-OH, and phenoxyl radical moieties, analogous to the chemistry carried out in heme-copper oxidases (HCOs). A 3D potential energy surface generated for this reaction reveals two possible reaction pathways: one involves nearly complete proton transfer (PT) from the phenol to the peroxo ligand before the barrier; the other involves O-O homolysis, where the phenol remains H-bonding to the peroxo OCu in the transition state (TS) and transfers the H+ after the barrier. In both mechanisms, electron transfer (ET) from phenol occurs after the PT (and after the barrier); therefore, only the interaction with the H+ is involved in lowering the O-O cleavage barrier. The relative barriers depend on covalency (which governs ET from Fe), and therefore vary with DFT functional. However, as these mechanisms differ by the amount of PT at the TS, kinetic isotope experiments were conducted to determine which mechanism is active. It is found that the phenolic proton exhibits a secondary kinetic isotope e...Continue Reading

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Citations

Aug 20, 2019·Chemical Communications : Chem Comm·Zachary ThammavongsyJenny Y Yang
Feb 10, 2021·Journal of the American Chemical Society·Fabian KruseInez M Weidinger
Feb 12, 2021·Chembiochem : a European Journal of Chemical Biology·Nicolò Zuin FantoniAndrew Kellett
May 31, 2019·Journal of the American Chemical Society·Andrew W SchaeferEdward I Solomon
Apr 6, 2018·Journal of the American Chemical Society·Kyle D SutherlinEdward I Solomon
Dec 16, 2020·Journal of the American Chemical Society·Asmita SinghaAbhishek Dey
Dec 5, 2017·Journal of the American Chemical Society·Colin W Anson, Shannon S Stahl
Mar 6, 2019·Journal of the American Chemical Society·Andrew W SchaeferEdward I Solomon
Jan 20, 2018·Chemical Reviews·Mårten WikströmVivek Sharma
Feb 7, 2018·Chemical Reviews·Michael L PegisJames M Mayer
Oct 30, 2018·Chemical Reviews·Suzanne M AdamKenneth D Karlin

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