期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2003
卷号：100
期号：7
页码：3623-3628
DOI：10.1073/pnas.0737180100
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：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[IMG]f1.gif" ALT="Formula" BORDER="0">) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F8)FeIII-(O[IMG]f2.gif" ALT="Formula" BORDER="0">)-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 {nu}(O-O) values observed in 4 and give rise to the novel structural features in 5.
