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Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/154620

An insight into transfer hydrogenation reactions catalysed by iridium(III) bis-N-heterocyclic carbenes

AutorGarcía, Néstor; Jaseer, E. A.; Munárriz, Julen; Sanz Miguel, Pablo J. ; Polo, Víctor; Iglesias, Manuel ; Oro, Luis A.
Palabras claveNitrogen heterocycles
Homogeneous catalysis
Transfer hydrogenation
Fecha de publicación2015
CitaciónEuropean Journal of Inorganic Chemistry (26): 4388-4395 (2015)
ResumenA variety of [M(L)2(L′)2{κC,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.
Versión del editorhttps://doi.org/10.1002/ejic.201500853
Identificadoresdoi: 10.1002/ejic.201500853
e-issn: 1099-0682
issn: 1434-1948
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