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http://hdl.handle.net/10261/154878
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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 | Osante, Iñaki | - |
dc.contributor.author | Cativiela, Carlos | - |
dc.contributor.author | López, José A. | - |
dc.contributor.author | Carmona, Daniel | - |
dc.date.accessioned | 2017-09-07T11:47:44Z | - |
dc.date.available | 2017-09-07T11:47:44Z | - |
dc.date.issued | 2016 | - |
dc.identifier | doi: 10.1039/C6DT02411D | - |
dc.identifier | e-issn: 1477-9234 | - |
dc.identifier | issn: 1477-9226 | - |
dc.identifier.citation | Dalton Transactions 45(36): 14203-14215 (2016) | - |
dc.identifier.uri | http://hdl.handle.net/10261/154878 | - |
dc.description.abstract | The modified cysteine ligand, S-benzyl-α-methyl-l-cysteine (HL2), was prepared from l-cysteine hydrochloride methyl ester. The reaction of commercial S-benzyl-l-cysteine (HL1) or HL2 with the dimer, [{(η-CMe)RhCl}(μ-Cl)], gives rise to the cationic complexes, [(η-CMe)RhCl(HL)]Cl (HL = HL1 (1), HL2 (2)), in which the cysteine ligand exhibits a κN,S coordination mode. In a basic medium, HL1 or HL2 reacts with [{(η-CMe)RhCl}(μ-Cl)] to afford mixtures of two epimers at the metal centre of the neutral complexes, [(η-CMe)RhCl(κN,O-L)] (HL = HL1 (3), HL2 (4)), in which amino carboxylate adopts a κN,O mode of coordination along with variable amounts of the cationic compounds, [(η-CMe)Rh(κN,O,S-L)]Cl (HL = HL1 (6Cl), HL2 (7Cl)), which contain κN,O,S coordinated cysteine-derived ligands. However, in a basic medium, the N-Boc substituted cysteine S-benzyl-N-Boc-l-cysteine (HL3) only yields the κO,S coordinated derivative, [(η-CMe)RhCl(κO,S-L3)] (5), as a mixture of two diastereomers depending on the configuration of the metal centre. The bidentate chelate complexes 3-5 react with AgSbF to give the hexafluoroantimonates [(η-CMe)Rh(κN,O,S-L)][SbF] (HL = HL1 (6Sb), HL2 (7Sb), HL3 (8Sb)) with tridentate coordination. Compound 8Sb reacts with NaHCO to give the neutral complex [(η-CMe)Rh(κN,O,S-L3)] (9), which can also be prepared by reacting the dimer [{(η-CMe)RhCl}(μ-Cl)] with HL3 in the presence of two equivalents of NaHCO. The new compounds contain up to four stereogenic centres, namely, Rh, S, N, and C. The absolute configuration of the complexes has been established by spectroscopic and diffractometric investigations, including the crystal structure determination of [(η-CMe)RhCl(κO,S-L3)] (5), [(η-CMe)Rh(κN,O,S-L1)][SbF] (6Sb), [(η-CMe)Rh(κN,O,S-L2)][SbF] (7Sb) and [(η-CMe)Rh(κN,O,S-L3)] (9). Variable temperature H NMR studies reveal the existence of epimerization processes and theoretical calculations were used to discriminate their nature. | - |
dc.description.sponsorship | We thank the Ministerio de Economía y Competitividad of Spain (CTQ2012-32095, CTQ2014-53033-P, CTQ2015-67366-P and CTQ2013-408555R) and Gobierno de Aragón and European Social Fund (Grupos Consolidados: Catalizadores Organometálicos Enantioselectivos, Aminoácidos y Péptidos and Inorganic Molecular Architecture) for financial support. This work was supported by the CONSOLIDER INGENIO 2010 program under the project “Factoría de Cristalización” (CSD2006-0015). M. C. acknowledges Diputación General de Aragón, CSIC and European Social Fund for a grant. R. R. and P. G. O. acknowledge CSIC, European Social Fund and Ministerio de Economía y Competitividad of Spain for a JAE and a 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/CTQ2013-408555-R | - |
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/CTQ2014-53033-P | - |
dc.relation.isversionof | Postprint | - |
dc.rights | openAccess | - |
dc.title | Half-sandwich complexes of rhodium containing cysteine-derived ligands | - |
dc.type | artículo | - |
dc.identifier.doi | 10.1039/C6DT02411D | - |
dc.relation.publisherversion | https://doi.org/10.1039/C6DT02411D | - |
dc.date.updated | 2017-09-07T11:47:44Z | - |
dc.description.version | Peer Reviewed | - |
dc.language.rfc3066 | eng | - |
dc.contributor.funder | Diputación General de Aragón | - |
dc.contributor.funder | Gobierno de Aragón | - |
dc.contributor.funder | Consejo Superior de Investigaciones Científicas (España) | - |
dc.contributor.funder | Ministerio de Economía y Competitividad (España) | - |
dc.contributor.funder | European Commission | - |
dc.relation.csic | Sí | - |
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/10.13039/501100003339 | 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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