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 Moenne-Loccoz, Christopher D. Incarvito, Arnold L. Rheingold, Marcus Honeckert, Susan Kaderli, Andreas D. Zuberbühler

Research output: Contribution to journalArticle

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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

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Electron Transport Complex IV
Heme
Copper
Ligands
Temperature
methylamine

ASJC Scopus subject areas

  • Genetics
  • General

Cite this

Superoxo, μ-peroxo, and μ-oxo complexes from heme/O2 and heme-Cu/O2 reactivity : Copper ligand influences in cytochrome c oxidase models. / Kim, Eunsuk; Helton, Matthew E.; Wasser, Ian M.; Karlin, Kenneth D.; Lu, Shen; Huang, Hong wei; Moenne-Loccoz, Pierre; Incarvito, Christopher D.; Rheingold, Arnold L.; Honeckert, Marcus; Kaderli, Susan; Zuberbühler, Andreas D.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 100, No. 7, 01.04.2003, p. 3623-3628.

Research output: Contribution to journalArticle

Kim, Eunsuk ; Helton, Matthew E. ; Wasser, Ian M. ; Karlin, Kenneth D. ; Lu, Shen ; Huang, Hong wei ; Moenne-Loccoz, Pierre ; Incarvito, Christopher D. ; Rheingold, Arnold L. ; Honeckert, Marcus ; Kaderli, Susan ; Zuberbühler, Andreas D. / Superoxo, μ-peroxo, and μ-oxo complexes from heme/O2 and heme-Cu/O2 reactivity : Copper ligand influences in cytochrome c oxidase models. In: Proceedings of the National Academy of Sciences of the United States of America. 2003 ; Vol. 100, No. 7. pp. 3623-3628.
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AU - Zuberbühler, Andreas D.

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