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| Content Provider | World Health Organization (WHO)-Global Index Medicus |
|---|---|
| Author | Sastri, Chivukula V. Lee, Jimin Nam, Wonwoo Lee, Junghyun Shin, Woonsup Lee, Yoon Jin Hirao, Hajime Jackson, Timothy A. Shaik, Sason Halfen, Jason A. Kim, Jinheung Que, Lawrence Oh, Kyungeun Ray, Kallol |
| Description | Author Affiliation: Sastri CV ( Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.); |
| Abstract | The reactivities of mononuclear nonheme iron(IV)-oxo complexes bearing different axial ligands, [Fe(IV)(O)(TMC)(X)](n+) [where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and X is NCCH(3) (1-NCCH(3)), CF(3)COO(-) (1-OOCCF(3)), or N(3)(-) (1-N(3))], and [Fe(IV)(O)(TMCS)](+) (1'-SR) (where TMCS is 1-mercaptoethyl-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane), have been investigated with respect to oxo-transfer to PPh(3) and hydrogen atom abstraction from phenol O H and alkylaromatic C H bonds. These reactivities were significantly affected by the identity of the axial ligands, but the reactivity trends differed markedly. In the oxidation of PPh(3), the reactivity order of 1-NCCH(3) > 1-OOCCF(3) > 1-N(3) > 1'-SR was observed, reflecting a decrease in the electrophilicity of iron(IV)-oxo unit upon replacement of CH(3)CN with an anionic axial ligand. Surprisingly, the reactivity order was inverted in the oxidation of alkylaromatic C H and phenol O H bonds, i.e., 1'-SR > 1-N(3) > 1-OOCCF(3) > 1-NCCH(3). Furthermore, a good correlation was observed between the reactivities of iron(IV)-oxo species in H atom abstraction reactions and their reduction potentials, E(p,c), with the most reactive 1'-SR complex exhibiting the lowest potential. In other words, the more electron-donating the axial ligand is, the more reactive the iron(IV)-oxo species becomes in H atom abstraction. Quantum mechanical calculations show that a two-state reactivity model applies to this series of complexes, in which a triplet ground state and a nearby quintet excited-state both contribute to the reactivity of the complexes. The inverted reactivity order in H atom abstraction can be rationalized by a decreased triplet-quintet gap with the more electron-donating axial ligand, which increases the contribution of the much more reactive quintet state and enhances the overall reactivity. |
| ISSN | 00278424 |
| e-ISSN | 10916490 |
| Journal | Proceedings of the National Academy of Sciences of the United States of America |
| Issue Number | 49 |
| Volume Number | 104 |
| Language | English |
| Publisher | National Academy of Sciences |
| Publisher Date | 2007-12-01 |
| Publisher Place | United States |
| Access Restriction | Open |
| Subject Keyword | Hydrogen Chemistry Nonheme Iron Proteins Oxygen Sulfhydryl Compounds Ligands Oxidation-Reduction Research Support, N.I.H., Extramural Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, Non-P.H.S. Multidisciplinary |
| Content Type | Text |
| Resource Type | Article |
| Subject | Multidisciplinary |
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