Sulfur K-Edge X-ray Absorption Spectroscopy and Density Functional Calculations on Mo(IV) and Mo(VI)-O Bis-dithiolenes: Insights into the Mechanism of Oxo Transfer in DMSO Reductase and Related Functional Analogues.
Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two Mo bis-dithiolene complexes, [Mo(OSi)(bdt)] and [MoO(OSi)(bdt)], where OSi = [OSiPhBu] and bdt = benzene-1,2-dithiolate(2-), that model the...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 24; pp. 8359 - 8372 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
6/23/2010
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=51699546&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 51699546 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/23/2010 vid: 132 iid: 24 pid: 997 pub: American Chemical Society artinfo: ui: 51699546 10.1021/ja910369c ppf: 8359 ppct: 13 formats: tig: atl: Sulfur K-Edge X-ray Absorption Spectroscopy and Density Functional Calculations on Mo(IV) and Mo(VI)-O Bis-dithiolenes: Insights into the Mechanism of Oxo Transfer in DMSO Reductase and Related Functional Analogues. aug: au: Tenderholt, Adam L. Jun-Jieh Wang Szilagyi, Robert K. Holm, Richard H. Hodgson, Keith O. Hedman, Britt Solomon, Edward I. affil: Department of Chemistry, Stanford University, Stanford, California 94305 Department of Chemistry and Chemical Biology, Harvard University, Cambridge Massachusetts 02138 Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025 su: Oxo process X-ray absorption near edge structure Density functionals Oxygen content of metal Molybdenum enzymes Ligands (Chemistry) Sulfur compounds sug: subj: Oxo process X-ray absorption near edge structure Density functionals Oxygen content of metal Molybdenum enzymes Ligands (Chemistry) Sulfur compounds ab: Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two Mo bis-dithiolene complexes, [Mo(OSi)(bdt)] and [MoO(OSi)(bdt)], where OSi = [OSiPhBu] and bdt = benzene-1,2-dithiolate(2-), that model the Mo(IV) and Mo(VI)-O states of the DMSO reductase family of molybdenum enzymes. These results show that the Mo(IV) complex undergoes metal-based oxidation unlike Mo tris-dithiolene complexes, indicating that the dithiolene ligands are behaving innocently. Experimentally validated calculations have been extended to model the oxo transfer reaction coordinate using dimethylsulfoxide (DMSO) as a substrate. The reaction proceeds through a transition state (TS1) to an intermediate with DMSO weakly bound, followed by a subsequent transition state (TS2) which is the largest barrier of the reaction. The factors that control the energies of these transition states, the nature of the oxo transfer process, and the role of the dithiolene ligand are discussed. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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