In:
Proceedings of the National Academy of Sciences, Proceedings of the National Academy of Sciences, Vol. 100, No. 7 ( 2003-04), p. 3623-3628
Abstract:
The O 2 -reaction chemistry of 1:1 mixtures of (F 8 )Fe II (1; F 8 = tetrakis(2,6-diflurorophenyl)porphyrinate) and [(L Me 2 N )Cu I ] + (2; L Me 2 N = 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 (F 8 )Fe III -(O \documentclass[12pt]{minimal} \usepackage{amsmath}
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\begin{document} \begin{equation*}{\mathrm{_{2}^{-}}}\end{equation*}\end{document} ) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F 8 )Fe III –(O \documentclass[12pt]{minimal} \usepackage{amsmath}
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\begin{document} \begin{equation*}{\mathrm{_{2}^{2-}}}\end{equation*}\end{document} )–Cu II (L Me 2 N )] + (4), which thermally converts to [(F 8 )Fe III –(O)–Cu II (L Me 2 N )] + (5), which has an unusually bent (Fe–O–Cu) bond moiety. Tridentate chelation, compared with tetradentate, is shown to dramatically lower the ν(O–O) values observed in 4 and give rise to the novel structural features in 5.
Type of Medium:
Online Resource
ISSN:
0027-8424
,
1091-6490
DOI:
10.1073/pnas.0737180100
Language:
English
Publisher:
Proceedings of the National Academy of Sciences
Publication Date:
2003
detail.hit.zdb_id:
209104-5
detail.hit.zdb_id:
1461794-8
SSG:
11
SSG:
12
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