000064331 001__ 64331
000064331 005__ 20230914083224.0
000064331 0247_ $$2doi$$a10.1039/c6dt02571d
000064331 0248_ $$2sideral$$a102712
000064331 037__ $$aART-2016-102712
000064331 041__ $$aeng
000064331 100__ $$aIturmendi, Amaia$$uUniversidad de Zaragoza
000064331 245__ $$aN-Heterocyclic olefins as ancillary ligands in catalysis: A study of their behaviour in transfer hydrogenation reactions
000064331 260__ $$c2016
000064331 5060_ $$aAccess copy available to the general public$$fUnrestricted
000064331 5203_ $$aThe Ir(I) complexes [Ir(cod)(¿P,C,P'-NHOPPh2)]PF6 and [IrCl(cod)(¿C-NHOOMe)] (cod = 1,5-cyclooctadiene, NHOPPh2 = 1,3-bis(2-(diphenylphosphanyl)ethyl)-2-methyleneimidazoline) and NHOOMe = 1,3-bis(2-(methoxyethyl)-2-methyleneimidazoline), both featuring an N-heterocyclic olefin ligand (NHO), have been tested in the transfer hydrogenation reaction; this representing the first example of the use of NHOs as ancillary ligands in catalysis. The pre-catalyst [Ir(cod)(¿P,C,P'-NHOPPh2)]PF6 has shown excellent activities in the transfer hydrogenation of aldehydes, ketones and imines using iPrOH as a hydrogen source, while [IrCl(cod)(¿C-NHOOMe)] decomposes throughout the reaction to give low yields of the hydrogenated product. Addition of one or two equivalents of a phosphine ligand to the latter avoids catalyst decomposition and significantly improves the reaction yields. The reaction mechanism has been investigated by means of stoichiometric studies and theoretical calculations. The formation of the active species ([Ir(¿P,C,P'-NHOPPh2)(iPrO)]) has been proposed to occur via isopropoxide coordination and concomitant COD dissociation. Moreover, throughout the catalytic cycle the NHO moiety behaves as a hemilabile ligand, thus allowing the catalyst to adopt stable square planar geometries in the transition states, which reduces the energetic barrier of the process.
000064331 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07$$9info:eu-repo/grantAgreement/ES/MEC/FPU14-06003$$9info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050
000064331 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000064331 590__ $$a4.029$$b2016
000064331 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2016$$dQ1$$eT1
000064331 592__ $$a1.229$$b2016
000064331 593__ $$aInorganic Chemistry$$c2016$$dQ1
000064331 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000064331 700__ $$aGarcía, Nestor
000064331 700__ $$aJaseer, E.A
000064331 700__ $$0(orcid)0000-0001-6089-6126$$aMunárriz, Julen$$uUniversidad de Zaragoza
000064331 700__ $$0(orcid)0000-0002-8220-6031$$aSanz Miguel, Pablo J.$$uUniversidad de Zaragoza
000064331 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, Victor$$uUniversidad de Zaragoza
000064331 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel$$uUniversidad de Zaragoza
000064331 700__ $$0(orcid)0000-0001-7154-7239$$aOro, Luis A.$$uUniversidad de Zaragoza
000064331 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000064331 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000064331 7102_ $$12010$$2X$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cProy. investigación HWA
000064331 773__ $$g45, 32 (2016), 12835-12845$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000064331 8564_ $$s783535$$uhttps://zaguan.unizar.es/record/64331/files/texto_completo.pdf$$yPostprint
000064331 8564_ $$s121013$$uhttps://zaguan.unizar.es/record/64331/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000064331 909CO $$ooai:zaguan.unizar.es:64331$$particulos$$pdriver
000064331 951__ $$a2023-09-13-10:42:45
000064331 980__ $$aARTICLE