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Superoxo, mu-peroxo, and mu-oxo complexes from heme/O2 and heme-Cu/O2 reactivity: copper ligand influences in cytochrome c oxidase models.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Kim, Eunsuk Helton, Matthew E. Wasser, Ian M. Karlin, Kenneth D. Lu, Shen Huang, Hong-Wei Moenne-Loccoz, Pierre Incarvito, Christopher D. Rheingold, Arnold L. Honecker, Marcus Kaderli, Susan Zuberbuhler, Andreas D. |
| Copyright Year | 2003 |
| 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(2)(-)) (3), whether or not 2 is present. Complex 3 subsequently reacts with 2 to form [(F(8))Fe(III)-(O(2)(2-))-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 nu(O-O) values observed in 4 and give rise to the novel structural features in 5. |
| Starting Page | 44 |
| Ending Page | 44 |
| Page Count | 1 |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | http://www.pnas.org/content/100/7/3623.full.pdf |
| PubMed reference number | 12655050v1 |
| Volume Number | 100 |
| Issue Number | 7 |
| Journal | Proceedings of the National Academy of Sciences of the United States of America |
| Language | English |
| Access Restriction | Open |
| Subject Keyword | CYTOCHROME C OXIDASE Cell Respiration Chelating Activity Copper Heme Iron Ligands mu-Chain Disease potassium oxonate |
| Content Type | Text |
| Resource Type | Article |
