000079138 001__ 79138
000079138 005__ 20231023123340.0
000079138 0247_ $$2doi$$a10.1039/c7cy02488f
000079138 0248_ $$2sideral$$a106594
000079138 037__ $$aART-2018-106594
000079138 041__ $$aeng
000079138 100__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.V.$$uUniversidad de Zaragoza
000079138 245__ $$aMechanistic studies on the: N -alkylation of amines with alcohols catalysed by iridium(i) complexes with functionalised N-heterocyclic carbene ligands
000079138 260__ $$c2018
000079138 5060_ $$aAccess copy available to the general public$$fUnrestricted
000079138 5203_ $$aIridium(i) cyclooctadiene complexes featuring O- and N-donor functionalised NHC ligands efficiently catalyse the C-N coupling of amines with alcohols through a borrowing hydrogen mechanism. These catalysts have been applied for the N-alkylation of several aromatic and aliphatic primary amines with a range of alcohols including benzyl alcohol derivatives, straight-chain primary alcohols and secondary alcohols. The cationic complex [Ir(NCCH3)(cod){MeIm(2-methoxybenzyl)}]+ (cod = 1, 5-cyclooctadiene, MeIm = 3-methylimidazol-2-ylidene) having a rigid O-donor wingtip exhibits the best catalytic performance for the N-alkylation of aniline with benzyl alcohol giving a quantitative conversion to N-benzylaniline in 3 h. Experimental and theoretical studies at the DFT level on the N-alkylation of aniline with benzyl alcohol catalysed by the model compound [IrCl(cod)(IMe)] (IMe = 1, 3-dimethyl-imidazol-2-ylidene) support the participation of the iridium catalyst not only in the alcohol dehydrogenation and imine hydrogenation steps but also in the key step leading to the formation of the new C-N bond. Nucleophilic attack of an iridium-amido species generated in basic medium on the electrophilic aldehyde results in a hemiaminolate intermediate species from which the hemiaminal is released by alcoholysis. The free hemiaminal dehydrates to give the corresponding intermediate imine product that is hydrogenated by the iridium catalyst to the N-alkylated amine product. The iridium(i) complexes featuring functionalised NHC ligands are more active than [IrCl(cod)(IMe)] which highlights the positive influence of the functional group on the N-alkylation catalytic activity.
000079138 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E07$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000079138 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000079138 590__ $$a5.726$$b2018
000079138 591__ $$aCHEMISTRY, PHYSICAL$$b32 / 147 = 0.218$$c2018$$dQ1$$eT1
000079138 592__ $$a1.734$$b2018
000079138 593__ $$aCatalysis$$c2018$$dQ1
000079138 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000079138 700__ $$aFernández-Tornos, J.
000079138 700__ $$0(orcid)0000-0001-7341-0033$$aGonzález-Lainez, M.$$uUniversidad de Zaragoza
000079138 700__ $$0(orcid)0000-0001-6675-7450$$aSánchez-Page, B.
000079138 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F.J.$$uUniversidad de Zaragoza
000079138 700__ $$0(orcid)0000-0001-7154-7239$$aOro, L.A.$$uUniversidad de Zaragoza
000079138 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J.J.$$uUniversidad de Zaragoza
000079138 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000079138 773__ $$g8, 9 (2018), 2381-2393$$pCATALYSIS SCIENCE & TECHNOLOGY$$tCatalysis Science and Technology$$x2044-4753
000079138 8564_ $$s555326$$uhttps://zaguan.unizar.es/record/79138/files/texto_completo.pdf$$yPostprint
000079138 8564_ $$s2268504$$uhttps://zaguan.unizar.es/record/79138/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000079138 909CO $$ooai:zaguan.unizar.es:79138$$particulos$$pdriver
000079138 951__ $$a2023-10-23-12:20:36
000079138 980__ $$aARTICLE