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dc.contributor.author | Carmona, María | es_ES |
dc.contributor.author | Rodríguez, Ricardo | es_ES |
dc.contributor.author | Méndez, Isabel | es_ES |
dc.contributor.author | Passarelli, Vincenzo | es_ES |
dc.contributor.author | Lahoz, Fernando J. | es_ES |
dc.contributor.author | García-Orduña, Pilar | es_ES |
dc.contributor.author | Carmona, Daniel | es_ES |
dc.date.accessioned | 2017-10-16T09:56:15Z | - |
dc.date.available | 2017-10-16T09:56:15Z | - |
dc.date.issued | 2017 | - |
dc.identifier.citation | Dalton Transactions 46(22): 7332-7350 (2017) | es_ES |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/10261/156295 | - |
dc.description.abstract | 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. | es_ES |
dc.description.sponsorship | 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. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Royal Society of Chemistry (UK) | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-66079-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/RYC-2013-13800 | - |
dc.relation.isversionof | Postprint | - |
dc.rights | openAccess | en_EN |
dc.title | Stereospecific control of the metal-centred chirality of rhodium(III) and iridium(III) complexes bearing tetradentate CNN′P ligands | es_ES |
dc.type | artículo | es_ES |
dc.description.peerreviewed | Peer reviewed | es_ES |
dc.relation.publisherversion | https://doi.org/10.1039/C7DT01446E | es_ES |
dc.identifier.e-issn | 1477-9234 | - |
dc.contributor.funder | Ministerio de Economía y Competitividad (España) | es_ES |
dc.contributor.funder | Gobierno de Aragón | es_ES |
dc.contributor.funder | Diputación General de Aragón | es_ES |
dc.contributor.funder | European Commission | es_ES |
dc.contributor.funder | Consejo Superior de Investigaciones Científicas (España) | es_ES |
dc.relation.csic | Sí | es_ES |
oprm.item.hasRevision | no ko 0 false | * |
dc.identifier.funder | http://dx.doi.org/10.13039/501100003339 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100000780 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100003329 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100010067 | es_ES |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.grantfulltext | open | - |
item.fulltext | With Fulltext | - |
item.languageiso639-1 | en | - |
item.cerifentitytype | Publications | - |
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