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

doi:10.1073/pnas.0737180100

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

Chemical Physiology and Biochemistry

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Abstract

The O₂-reaction chemistry of 1:1 mixtures of (F₈)Fe^II (1; F₈ = tetrakis(2,6-diflurorophenyl)porphyrinate) and [(L^Me2N)Cu^I]⁺ (2; L^Me2N = 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)Fe^III-(O^-₂) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F₈)Fe^III- (O^2-₂)-Cu^II(L^Me2N)]⁺ (4), which thermally converts to [(F₈)Fe^III- (O)-Cu^II(L^Me2N)]⁺ (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 language	English (US)
Pages (from-to)	3623-3628
Number of pages	6
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	100
Issue number	7
DOIs	https://doi.org/10.1073/pnas.0737180100
State	Published - Apr 1 2003

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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

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. et al.
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 journal › Article › peer-review

Kim, E, Helton, ME, Wasser, IM, Karlin, KD, Lu, S, Huang, HW, Moënne-Loccoz, P, Incarvito, CD, Rheingold, AL, Honeckert, M, Kaderli, S & Zuberbühler, AD 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, vol. 100, no. 7, pp. 3623-3628. https://doi.org/10.1073/pnas.0737180100

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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.",

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T1 - Superoxo, μ-peroxo, and μ-oxo complexes from heme/O2 and heme-Cu/O2 reactivity

T2 - Copper ligand influences in cytochrome c oxidase models

AU - Kim, Eunsuk

AU - Helton, Matthew E.

AU - Wasser, Ian M.

AU - Karlin, Kenneth D.

AU - Lu, Shen

AU - Huang, Hong wei

AU - Moënne-Loccoz, Pierre

AU - Incarvito, Christopher D.

AU - Rheingold, Arnold L.

AU - Honeckert, Marcus

AU - Kaderli, Susan

AU - Zuberbühler, Andreas D.

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N2 - 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.

AB - 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.

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

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