Superoxo, Mu-peroxo, and Mu-oxo Complexes from Heme/O2 and Heme-Cu/O2 Reactivity: Copper Ligand Influences in Cytochrome C Oxidase Models

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2003 Mar 26

PMID 12655050

Citations 25

Authors

Eunsuk Kim

Matthew E Helton

Ian M Wasser

Kenneth D Karlin

Shen Lu

Hong-Wei Huang

Pierre Moenne-Loccoz

Christopher D Incarvito

Arnold L Rheingold

Marcus Honecker

Susan Kaderli

Andreas D Zuberbuhler

Affiliations

Soon will be listed here.

Abstract

The O(2)-reaction chemistry of 1:1 mixtures of (F(8))Fe(II) (1; F(8) = tetrakis(2,6-diflurorophenyl)porphyrinate) and [(L(Me(2))N)Cu(I)](+) (2; L(Me(2))N = N,N-bis(2-[2-(N',N'-4-dimethylamino)pyridyl]ethyl)methylamine) is described, to model aspects of the chemistry occurring in cytochrome c oxidase. Spectroscopic investigations, along with stopped-flow kinetics, reveal that low-temperature oxygenation of 1/2 leads to rapid formation of a heme-superoxo species (F(8))Fe(III)-(O(2)(-)) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F(8))Fe(III)-(O(2)(2-))-Cu(II)(L(Me(2))N)](+) (4), which thermally converts to [(F(8))Fe(III)-(O)-Cu(II)(L(Me(2))N)](+) (5), which has an unusually bent (Fe-O-Cu) bond moiety. Tridentate chelation, compared with tetradentate, is shown to dramatically lower the nu(O-O) values observed in 4 and give rise to the novel structural features in 5.

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