An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes

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...

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Detalles Bibliográficos
Autores: García, N., Jaseer, E.A., Munarriz, J., Sanz Miguel, P.J., Polo, V., Iglesias, M., Oro, L.A.
Tipo de recurso: artículo
Estado:Versión enviada para evaluación y publicación
Fecha de publicación:2015
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:56357
Acceso en línea:http://zaguan.unizar.es/record/56357
Access Level:acceso abierto
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spelling An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenesGarcía, N.Jaseer, E.A.Munarriz, J.Sanz Miguel, P.J.Polo, V.Iglesias, M.Oro, L.A.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.2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/submittedVersionapplication/pdfhttp://zaguan.unizar.es/record/56357reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E07info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenioinfo:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenioinfo:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenioinfo:eu-repo/semantics/openAccessoai:zaguan.unizar.es:563572026-05-29T13:59:51Z
dc.title.none.fl_str_mv An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
title An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
spellingShingle An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
García, N.
title_short An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
title_full An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
title_fullStr An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
title_full_unstemmed An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
title_sort An insight into transfer hydrogenation reactions catalysed by iridium(iii) bis-n-heterocyclic carbenes
dc.creator.none.fl_str_mv García, N.
Jaseer, E.A.
Munarriz, J.
Sanz Miguel, P.J.
Polo, V.
Iglesias, M.
Oro, L.A.
author García, N.
author_facet García, N.
Jaseer, E.A.
Munarriz, J.
Sanz Miguel, P.J.
Polo, V.
Iglesias, M.
Oro, L.A.
author_role author
author2 Jaseer, E.A.
Munarriz, J.
Sanz Miguel, P.J.
Polo, V.
Iglesias, M.
Oro, L.A.
author2_role author
author
author
author
author
author
description 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.
publishDate 2015
dc.date.none.fl_str_mv 2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/submittedVersion
format article
status_str submittedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/56357
url http://zaguan.unizar.es/record/56357
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA/E07
info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio
info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio
info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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