Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 100, Issue 7, Pages 3623-3628Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0737180100
Keywords
-
Categories
Funding
- NIGMS NIH HHS [GM18865, GM60353, GM20805, R01 GM018865, F32 GM020805, R01 GM060353] Funding Source: Medline
Ask authors/readers for more resources
The O-2-reaction chemistry of 1:1 mixtures of (F-8)Fe-11 (1; F-8 = tetrakis(2,6-diflurorophenyl)porphyrinate) and [(L-Me2N)Cu-1](+) (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 (F-8)Fe-111_ (O-2(-)) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F-8)Fe-111_(O-2(2-))-Cu-11(L-Me2N)](+) (4), which thermally converts to [(F-8)Fe (111-)(O)-Cu-11(L-Me2N)](+) (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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available