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dc.contributor.authorCabeza, Javier A.-
dc.contributor.authorRío, Ignacio del-
dc.contributor.authorFernández-Colinas, José M.-
dc.contributor.authorPérez-Carreño, E.-
dc.contributor.authorSánchez-Vega, M. Gabriela-
dc.contributor.authorVázquez-García, Digna-
dc.identifier.citationOrganometallics 29(17): 3828-3836 (2010)es_ES
dc.description9 páginas, 6 figuras, 1 esquema, 3 tablas.es_ES
dc.description.abstractThe unsaturated triosmium dihydrido cluster [Os3(μ-H)2(CO)10] (1) reacts at room temperature with N-heterocyclic carbenes (NHCs) of the 1,3-disubstituted imidazol-2-ylidene type (R1R2Im). While the addition product [Os3H(μ-H)(NHC)(CO)10] has been obtained only for NHC = Mes2Im, CO-substitution derivatives of the type [Os3(μ-H)2(NHC)(CO)9] have been obtained for NHC = Me2Im, MePhIm, Ph2Im, and Mes2Im. Small amounts of the hydroxo-bridged derivatives [Os3(μ-H)(μ-OH)(NHC)(CO)9] (NHC = Me2Im, MePhIm) are also formed in wet solvents. DFT mechanistic studies on the reactions of compound 1 with the small Me2Im and the very bulky Mes2Im have revealed that the substitution reactions follow an associative reaction pathway that starts with the addition of the NHC to compound 1 (in one elementary step that gives [Os3H(μ-H)(NHC)(CO)10]) and ends with the elimination of a CO ligand (in three steps from [Os3H(μ-H)(NHC)(CO)10]) to give the final substitution product [Os3(μ-H)(μ-OH)(NHC)(CO)9]. The relative energy of each stationary point depends upon the NHC ligand used, those of the Mes2Im system being higher than those of the Me2Im system. This computational study has also explained why the addition intermediate [Os3H(μ-H)(NHC)(CO)10] has been isolated only for NHC = Mes2Im.es_ES
dc.description.sponsorshipThis work has been supported by the European Union (FEDER grants), the Spanish MICINN (projects CTQ2007-60865 and MAT2006-1997), and the Government of Principado de Asturias (project IB09-093). Fellowships toM.G.S.-V. (from the University of Carabobo, Venezuela) and D.V.-G. (from Xunta de Galicia, Spain) are also acknowledged.es_ES
dc.publisherAmerican Chemical Societyes_ES
dc.titleReactivity of [Os3(μ-H)2(CO)10] with N-Heterocyclic carbenes: A combined experimental and DFT computational studyes_ES
dc.description.peerreviewedPeer reviewedes_ES
dc.contributor.funderEuropean Commission-
dc.contributor.funderMinisterio de Ciencia e Innovación (España)-
dc.contributor.funderPrincipado de Asturias-
dc.contributor.funderUniversidad de Carabobo-
dc.contributor.funderXunta de Galicia-
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