Theoretical study of the proton transfer between water and [FeH(CO)(4)](-)in aqueous solution and relevance to the water-gas shift reaction catalyzed by iron pentacarbonyl in the condensed phase

Citation
C. Amovilli et al., Theoretical study of the proton transfer between water and [FeH(CO)(4)](-)in aqueous solution and relevance to the water-gas shift reaction catalyzed by iron pentacarbonyl in the condensed phase, ORGANOMETAL, 20(7), 2001, pp. 1310-1316
Citations number
20
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
7
Year of publication
2001
Pages
1310 - 1316
Database
ISI
SICI code
0276-7333(20010402)20:7<1310:TSOTPT>2.0.ZU;2-W
Abstract
Proton transfer between H2O and FeH(CO)(4)(-), the assumed slow step of the water-gas shift reaction catalyzed by Fe(CO)(5), has been studied with Har tree-Fock and multiconfiguration CASSCF ab initio methods. The calculations have been performed in vacuo and in water solution at 298 K, simulating th e solvent as a polarizable continuum medium. The process in solution has be en found to be less endothermic than in the gas phase by about 50 kcal/mol. The valence bond analysis, made on the CASSCF wave function along the reac tion path, explains the mechanism in terms of a single structure in which t he transferred hydrogen is simultaneously bonded to iron and oxygen with a different polarization depending on the reaction coordinate.