Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands

Ligands LH1–LH3 have been prepared by two successive condensation/reduction steps. These ligands react with MCl3 (M = Rh, Ir) rendering the trichlorido complexes [MCl3(κ3N,N’,P-LH)] (M = Rh, LH = LH1 (1), LH2 (2), LH3 (3); M = Ir, LH = LH1, (4)) as racemic mixtures of fac and mer isomers. Only one o...

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Autores: Carmona, María, Rodríguez Martínez, Ricardo, Méndez, Isabel, Passarelli, Vincenzo, Lahoz, Fernando J., García-Orduña, Pilar, Carmona, Daniel
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/156295
Acceso en línea:http://hdl.handle.net/10261/156295
Access Level:acceso abierto
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spelling Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligandsCarmona, MaríaRodríguez Martínez, RicardoMéndez, IsabelPassarelli, VincenzoLahoz, Fernando J.García-Orduña, PilarCarmona, DanielLigands LH1–LH3 have been prepared by two successive condensation/reduction steps. These ligands react with MCl3 (M = Rh, Ir) rendering the trichlorido complexes [MCl3(κ3N,N’,P-LH)] (M = Rh, LH = LH1 (1), LH2 (2), LH3 (3); M = Ir, LH = LH1, (4)) as racemic mixtures of fac and mer isomers. Only one of the two possible fac isomers was detected. The mer isomer of the rhodium compounds 1–3 quantitatively isomerizes to the more stable fac isomer, whereas the mer isomer of the iridium complex 4 does not. DFT calculations indicate a dissociative pathway for this isomerization. In the presence of acetate or trifluoroacetate, complexes 1–3 or 4, respectively, undergo cyclometallation of their free benzylic arm affording the corresponding dichlorido compounds [MCl2(κ4C,N,N’,P-L)] (M = Rh, L = L1 (5), L2 (6), L3 (7); M = Ir, L = L1 (8)). Only one of the three possible enantiomeric pairs of coordination isomers was detected. The configuration at the stereogenic centres, namely the metal and the iminic nitrogen atom is stereospecifically predetermined. DFT calculations reveal that the cyclometallation follows an acetateassisted mechanism and indicate that the isolated isomers are the most stable. Complexes 1–8 have been characterized by analytical and spectroscopic means and by the determination of the crystal structures of the complexes 1, 3 and 5–8 by X-ray diffractometry.We thank the Ministerio de Economía y Competitividad of Spain (CTQ2015-66079-P) and Gobierno de Aragón (Grupo Consolidado E-63: Catalizadores Organometálicos Enantioselectivos) for financial support. M. C. acknowledges Diputación General de Aragón, CSIC and European Social Fund for a grant. R. R. acknowledges the Ministerio de Economía y Competitividad of Spain for a Ramón y Cajal (RYC-2013-13800) grant. P. G.-O. acknowledges CSIC, European Social Fund and Ministerio de Economía y Competitividad of Spain for a PTA contract.Peer reviewedRoyal Society of Chemistry (UK)Ministerio de Economía y Competitividad (España)Gobierno de AragónDiputación General de AragónEuropean CommissionConsejo Superior de Investigaciones Científicas (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201720172017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/156295reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-66079-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/RYC-2013-13800https://doi.org/10.1039/C7DT01446ESíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1562952026-05-22T06:33:51Z
dc.title.none.fl_str_mv Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
title Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
spellingShingle Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
Carmona, María
title_short Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
title_full Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
title_fullStr Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
title_full_unstemmed Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
title_sort Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands
dc.creator.none.fl_str_mv Carmona, María
Rodríguez Martínez, Ricardo
Méndez, Isabel
Passarelli, Vincenzo
Lahoz, Fernando J.
García-Orduña, Pilar
Carmona, Daniel
author Carmona, María
author_facet Carmona, María
Rodríguez Martínez, Ricardo
Méndez, Isabel
Passarelli, Vincenzo
Lahoz, Fernando J.
García-Orduña, Pilar
Carmona, Daniel
author_role author
author2 Rodríguez Martínez, Ricardo
Méndez, Isabel
Passarelli, Vincenzo
Lahoz, Fernando J.
García-Orduña, Pilar
Carmona, Daniel
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Gobierno de Aragón
Diputación General de Aragón
European Commission
Consejo Superior de Investigaciones Científicas (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Ligands LH1–LH3 have been prepared by two successive condensation/reduction steps. These ligands react with MCl3 (M = Rh, Ir) rendering the trichlorido complexes [MCl3(κ3N,N’,P-LH)] (M = Rh, LH = LH1 (1), LH2 (2), LH3 (3); M = Ir, LH = LH1, (4)) as racemic mixtures of fac and mer isomers. Only one of the two possible fac isomers was detected. The mer isomer of the rhodium compounds 1–3 quantitatively isomerizes to the more stable fac isomer, whereas the mer isomer of the iridium complex 4 does not. DFT calculations indicate a dissociative pathway for this isomerization. In the presence of acetate or trifluoroacetate, complexes 1–3 or 4, respectively, undergo cyclometallation of their free benzylic arm affording the corresponding dichlorido compounds [MCl2(κ4C,N,N’,P-L)] (M = Rh, L = L1 (5), L2 (6), L3 (7); M = Ir, L = L1 (8)). Only one of the three possible enantiomeric pairs of coordination isomers was detected. The configuration at the stereogenic centres, namely the metal and the iminic nitrogen atom is stereospecifically predetermined. DFT calculations reveal that the cyclometallation follows an acetateassisted mechanism and indicate that the isolated isomers are the most stable. Complexes 1–8 have been characterized by analytical and spectroscopic means and by the determination of the crystal structures of the complexes 1, 3 and 5–8 by X-ray diffractometry.
publishDate 2017
dc.date.none.fl_str_mv 2017
2017
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/156295
url http://hdl.handle.net/10261/156295
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-66079-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/RYC-2013-13800
https://doi.org/10.1039/C7DT01446E
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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