Mechanisms for CO Production from CO Using Reduced Rhenium Tricarbonyl Catalysts.
The chemical conversion of CO has been studied by numerous experimental groups. Particularly the use of rhenium tricarbonyl-based molecular catalysts has attracted interest owing to their ability to absorb light, store redox equivalents, and convert CO into higher-energy products. The mechanism by w...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 11; pp. 5180 - 5187 |
|---|---|
| Autores principales: | , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
3/21/2012
|
| 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=73940608&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 73940608 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: 3/21/2012 vid: 134 iid: 11 pid: 997 pub: American Chemical Society artinfo: ui: 73940608 10.1021/ja2105834 ppf: 5180 ppct: 7 formats: tig: atl: Mechanisms for CO Production from CO Using Reduced Rhenium Tricarbonyl Catalysts. aug: au: Agarwal, Jay Fujita, Etsuko Schaefer III, Henry F. Muckerman, James T. affil: Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United States su: Chemical reduction Carbon dioxide Rhenium catalysts Density functionals Carbon monoxide Chemical engineering sug: subj: Chemical reduction Carbon dioxide Rhenium catalysts Density functionals Carbon monoxide Chemical engineering ab: The chemical conversion of CO has been studied by numerous experimental groups. Particularly the use of rhenium tricarbonyl-based molecular catalysts has attracted interest owing to their ability to absorb light, store redox equivalents, and convert CO into higher-energy products. The mechanism by which these catalysts mediate reduction, particularly to CO and HCOO, is poorly understood, and studies aimed at elucidating the reaction pathway have likely been hindered by the large number of species present in solution. Herein the mechanism for carbon monoxide production using rhenium tricarbonyl catalysts has been investigated using density functional theory. The investigation presented proceeds from the experimental work of Meyer's group (J. Chem. Soc., Chem. Commun.1985, 1414-1416) in DMSO and Fujita's group (J. Am. Chem. Soc.2003, 125, 11976-11987) in dry DMF. The latter work with a simplified reaction mixture, one that removes the photo-induced reduction step with a sacrificial donor, is used for validation of the proposed mechanism, which involves formation of a rhenium carboxylate dimer, [Re(dmb)(CO)](OCO), where dmb = 4,4′-dimethyl-2,2′-bipyridine. CO insertion into this species, and subsequent rearrangement, is proposed to yield CO and the carbonate-bridged [Re(dmb)(CO)](OCO). Structures and energies for the proposed reaction path are presented and compared to previously published experimental observations. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
|---|