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http://hdl.handle.net/10261/155829
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dc.contributor.author | Carmona, María | - |
dc.contributor.author | Rodríguez, Ricardo | - |
dc.contributor.author | Lahoz, Fernando J. | - |
dc.contributor.author | García-Orduña, Pilar | - |
dc.contributor.author | Cativiela, Carlos | - |
dc.contributor.author | López, José A. | - |
dc.contributor.author | Carmona, Daniel | - |
dc.date.accessioned | 2017-09-29T07:05:16Z | - |
dc.date.available | 2017-09-29T07:05:16Z | - |
dc.date.issued | 2017 | - |
dc.identifier | doi: 10.1039/C6DT04341K | - |
dc.identifier | e-issn: 1477-9234 | - |
dc.identifier | issn: 1477-9226 | - |
dc.identifier.citation | Dalton Transactions 46(3): 962-976 (2017) | - |
dc.identifier.uri | http://hdl.handle.net/10261/155829 | - |
dc.description.abstract | The dimers [{(η-ring)MCl}(μ-Cl)] ((η-ring)M = (η-CMe)Ir, (η-p-MeCHiPr)Ru) react with the modified cysteines S-benzyl-l-cysteine (HL1) or S-benzyl-α-methyl-l-cysteine (HL2) affording cationic complexes of the formula [(η-ring)MCl(κN,S-HL)]Cl (1, 2) in good yield. Addition of NaHCO to complexes 1 and 2 gave equilibrium mixtures of neutral [(η-ring)MCl(κN,O-L)] (3, 4) and cationic [(η-ring)M(κN,O,S-L)]Cl (6Cl, 7Cl) complexes. Similar mixtures were obtained in one-pot reaction by successive addition of the modified cysteine and NaHCO to the above formulated dimers. Addition of the N-Boc substituted cysteine derivative S-benzyl-N-Boc-l-cysteine (HL3) and NaHCO to the dimers [{(η-ring)MCl}(μ-Cl)] affords the neutral compounds [(η-ring)MCl(κO,S-L3)] ((η-ring)M = (η-CMe)Ir (5a), (η-p-MeCHiPr)Ru (5b)). Complexes of the formula [(η-ring)MCl(κN,O,S-L)][SbF] (6Sb-8Sb), in which the cysteine derivative acts as a tridentate chelate ligand, can be prepared by adding one equivalent of AgSbF to the solutions of compounds 5 or to the mixtures of complexes 3/6Cl and 4/7Cl. The amide proton of compounds 8aSb and 8bSb can be removed by addition of NaHCO affording the neutral complexes [(η-ring)M(κN,O,S-L3)] ((η-ring)M = (η-CMe)Ir (9a), (η-p-MeCHiPr)Ru (9b)). Complexes 9a and 9b can also be prepared by reacting the dimers [{(η-ring)MCl}(μ-Cl)] with HL3 and two equivalents of NaHCO. The absolute configuration of the complexes has been established by spectroscopic and diffractometric means including the crystal structure determination of (R,R,R)-[(η-CMe)Ir(κN,O,S-L1)][SbF] (6aSb). The thermodynamic parameters associated with the epimerization at sulphur that the iridium compound [(η-CMe)Ir(κN,O,S-L3)] (9a) undergoes have been determined through variable temperature H NMR studies. | - |
dc.description.sponsorship | We thank the Ministerio de Economía y Competitividad of Spain (CTQ2012-32095, CTQ2013-40855-R and CTQ2015-67366-P) Gobierno de Aragón and the European Social Fund (Grupos Consolidados: Catalizadores Organometálicos Enantioselectivos, Aminoácidos y Péptidos and Inorganic Molecular Architecture) for financial support. M. C. acknowledges Diputación General de Aragón, CSIC and the European Social Fund for a grant. R. R. and P. G. O. acknowledge CSIC, the European Social Fund and the Ministerio de Economía y Competitividad of Spain for the JAE and Ramón y Cajal (RYC-2013-13800) grants and for a PTA contract, respectively. | - |
dc.publisher | Royal Society of Chemistry (UK) | - |
dc.relation | info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-67366-P | - |
dc.relation | info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-40855-R | - |
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 | Half-sandwich complexes of iridium and ruthenium containing cysteine-derived ligands | - |
dc.type | artículo | - |
dc.identifier.doi | 10.1039/C6DT04341K | - |
dc.relation.publisherversion | https://doi.org/10.1039/C6DT04341K | - |
dc.date.updated | 2017-09-29T07:05:17Z | - |
dc.description.version | Peer Reviewed | - |
dc.language.rfc3066 | eng | - |
dc.contributor.funder | Consejo Superior de Investigaciones Científicas (España) | - |
dc.contributor.funder | Diputación General de Aragón | - |
dc.contributor.funder | European Commission | - |
dc.contributor.funder | Ministerio de Economía y Competitividad (España) | - |
dc.contributor.funder | Gobierno de Aragón | - |
dc.relation.csic | Sí | - |
dc.identifier.funder | http://dx.doi.org/10.13039/501100003329 | es_ES |
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/10.13039/501100010067 | es_ES |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.grantfulltext | open | - |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | With Fulltext | - |
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