56357 20230914083220.0 doi 10.1002/ejic.201500853 sideral 92000 ART-2015-92000 eng García, N. An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes 2015 Access copy available to the general public Unrestricted A variety of [M(L)2(L')2{kC,C'-bis(NHC)}]BF4 complexes (M = Rh or Ir; L = CH3CN or wingtip group; L' = I– or CF3COO–; NHC=N-heterocyclic carbene) have been tested as pre-catalysts for the transfer hydrogenation of ketones and imines. The conversions and TOF's obtained are closely related to the nature of the ligand system and metal centre, more strongly coordinating wingtip groups yielding more active and recyclable catalysts. Theoretical calculations at the DFT level support a classic stepwise metal-hydride pathway against the concerted Meerwein–Ponndorf–Verley (MPV) mechanism. The calculated catalytic cycle involves a series of ligand rearrangements due to the high trans effect of the carbene and hydrido ligands, which are more stable when situated in mutual cis positions. The reaction profiles obtained for the complexes featuring an iodide or a trifluoroacetate in one of the apical positions agree well with the relative activity observed for both catalysts. info:eu-repo/grantAgreement/ES/DGA/E07 info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CTQ2011-27593 info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CTQ2012-35665 info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2009-0050 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 2.686 2015 CHEMISTRY, INORGANIC & NUCLEAR 12 / 46 = 0.261 2015 Q2 T1 0.983 2015 Inorganic Chemistry 2015 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/submittedVersion Jaseer, E.A. Munarriz, J. Universidad de Zaragoza (orcid)0000-0001-6089-6126 Sanz Miguel, P.J. Universidad de Zaragoza (orcid)0000-0002-8220-6031 Polo, V. Universidad de Zaragoza (orcid)0000-0001-5823-7965 Iglesias, M. Universidad de Zaragoza (orcid)0000-0003-3144-5320 Oro, L.A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 2015, 26 (2015), 4388-4395 Eur. j. inorg. chem. European Journal of Inorganic Chemistry 1434-1948 845869 http://zaguan.unizar.es/record/56357/files/texto_completo.pdf Preprint 118581 http://zaguan.unizar.es/record/56357/files/texto_completo.jpg?subformat=icon icon Preprint oai:zaguan.unizar.es:56357 articulos driver 2023-09-13-10:40:17 ARTICLE