TY - JOUR
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.
PY - 2003/4/1
Y1 - 2003/4/1
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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U2 - 10.1073/pnas.0737180100
DO - 10.1073/pnas.0737180100
M3 - Article
C2 - 12655050
AN - SCOPUS:0037384039
SN - 0027-8424
VL - 100
SP - 3623
EP - 3628
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 7
ER -