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dc.contributor.authorJiménez, M. Victoria-
dc.contributor.authorFernández-Tornos, Javier-
dc.contributor.authorPérez-Torrente, Jesús J.-
dc.contributor.authorModrego, Francisco J.-
dc.contributor.authorWinterle, Sonja-
dc.contributor.authorCunchillos, Carmen-
dc.contributor.authorLahoz, Fernando J.-
dc.contributor.authorOro, Luis A.-
dc.date.accessioned2012-10-15T09:55:39Z-
dc.date.available2012-10-15T09:55:39Z-
dc.date.issued2011-09-
dc.identifier.citationOrganometallics 30(20): 5493-5508 (2011)es_ES
dc.identifier.issn0276-7333-
dc.identifier.urihttp://hdl.handle.net/10261/57986-
dc.description16 páginas, 5 figuras, 3 tablas, 3 esquemas.es_ES
dc.description.abstractA series of neutral and cationic rhodium and iridium(I) complexes based on hemilabile O-donor- and N-donor-functionalized NHC ligands having methoxy, dimethylamino, and pyridine as donor functions have been synthesized. The hemilabile fragment is coordinated to the iridium center in the cationic complexes [Ir(cod)(MeImR)]+ (R = pyridin-2-ylmethyl, 3-dimethylaminopropyl) but remains uncoordinated in the complexes [MBr(cod)(MeImR)], [M(NCCH3)(cod)(MeImR)]+ (M = Rh, Ir; R = 2-methoxyethyl and 2-methoxybenzyl) and [IrX(cod)(MeImR)] (X = Br, R = pyridin-2-ylmethyl; X = Cl, R = 2-dimethylaminoethyl, 3-dimethylaminopropyl). The structure of [IrBr(cod)(MeIm(2-methoxybenzyl))] has been determined by X-ray diffraction. The iridium complexes are efficient precatalysts for the transfer hydrogenation of cyclohexanone in 2-propanol/KOH. A comparative study has shown that cationic complexes are more efficient than the neutral and also that complexes having O-functionalized NHC ligands provide much more active systems than the corresponding N-functionalized ligands with TOFs up to 4600 h–1. The complexes [Ir(NCCH3)(cod)(MeImR)]+ (R = 2-methoxyethyl and 2-methoxybenzyl) have been successfully applied to the reduction of several unsaturated substrates as ketones, aldehydes, α,β-unsaturated ketones, and imines. The investigation of the reaction mechanism by NMR and MS has allowed the identification of relevant alkoxo intermediates [Ir(OR)(cod)(MeImR)] and the unsaturated hydride species [IrH(cod)(MeImR)]. The β-H elimination in the alkoxo complex [Ir(OiPr)(cod)(MeIm(2-methoxybenzyl))] leading to hydrido species has been studied by DFT calculations. An interaction between the β-H on the alkoxo ligand and the oxygen atom of the methoxy fragment of the NHC ligand, which results in a net destabilization of the alkoxo intermediate by a free energy of +1.0 kcal/mol, has been identified. This destabilization facilitates the β-H elimination step in the catalytic process and could explain the positive effect of the methoxy group of the functionalized NHC ligands on the catalytic activity.es_ES
dc.description.sponsorshipFinancial support from Ministerio de Ciencia e Innovación (MICINN/FEDER) is gratefully acknowledged (Projects: CTQ2010-15221, CSD2006-0015, and CSD2009-00050). J.F. T. thanks the Spanish MICINN for a predoctoral fellowship, and S.W. thanks the Eramus program (Univ. RWTH-Aachen, Germany).es_ES
dc.language.isoenges_ES
dc.publisherAmerican Chemical Societyes_ES
dc.relation.isversionofPostprint-
dc.rightsopenAccesses_ES
dc.titleIridium(I) complexes with hemilabile N-heterocyclic carbenes: Efficient and versatile transfer hydrogenation catalystses_ES
dc.typeartículoes_ES
dc.identifier.doi10.1021/om200747k-
dc.description.peerreviewedPeer reviewedes_ES
dc.relation.publisherversionhttp://dx.doi.org/10.1021/om200747kes_ES
dc.identifier.e-issn1520-6041-
dc.contributor.funderMinisterio de Ciencia e Innovación (España)-
dc.contributor.funderRWTH Aachen University-
dc.contributor.funderEuropean Commission-
dc.relation.csic-
dc.identifier.funderhttp://dx.doi.org/10.13039/501100004837es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100007210es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100000780es_ES
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