Superoxo, μ-peroxo, and μ-oxo complexes from heme/O2 and heme-Cu/O2 reactivity: Copper ligand influences in cytochrome c oxidase models

Eunsuk Kim, Matthew E. Helton, Ian M. Wasser, Kenneth D. Karlin, Shen Lu, Hong wei Huang, Pierre Moënne-Loccoz, Christopher D. Incarvito, Arnold L. Rheingold, Marcus Honeckert, Susan Kaderli, Andreas D. Zuberbühler

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Abstract

The O2-reaction chemistry of 1:1 mixtures of (F8)FeII (1; F8 = tetrakis(2,6-diflurorophenyl)porphyrinate) and [(LMe2N)CuI]+ (2; LMe2N = 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 (F8)FeIII-(O-2) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F8)FeIII- (O2-2)-CuII(LMe2N)]+ (4), which thermally converts to [(F8)FeIII- (O)-CuII(LMe2N)]+ (5), which has an unusually bent (Fe-O-Cu) bond moiety. Tridentate chelation, compared with tetradentate, is shown to dramatically lower the v(O-O) values observed in 4 and give rise to the novel structural features in 5.

Original languageEnglish (US)
Pages (from-to)3623-3628
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume100
Issue number7
DOIs
StatePublished - Apr 1 2003

ASJC Scopus subject areas

  • General

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    Kim, E., Helton, M. E., Wasser, I. M., Karlin, K. D., Lu, S., Huang, H. W., Moënne-Loccoz, P., Incarvito, C. D., Rheingold, A. L., Honeckert, M., Kaderli, S., & Zuberbühler, A. D. (2003). Superoxo, μ-peroxo, and μ-oxo complexes from heme/O2 and heme-Cu/O2 reactivity: Copper ligand influences in cytochrome c oxidase models. Proceedings of the National Academy of Sciences of the United States of America, 100(7), 3623-3628. https://doi.org/10.1073/pnas.0737180100