000061914 001__ 61914
000061914 005__ 20231027130637.0
000061914 0247_ $$2doi$$a10.1039/c6dt02411d
000061914 0248_ $$2sideral$$a96790
000061914 037__ $$aART-2016-96790
000061914 041__ $$aeng
000061914 100__ $$0(orcid)0000-0002-2343-0156$$aCarmona, M.
000061914 245__ $$aHalf-sandwich complexes of rhodium containing cysteine-derived ligands
000061914 260__ $$c2016
000061914 5060_ $$aAccess copy available to the general public$$fUnrestricted
000061914 5203_ $$aThe 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, [{(η5-C5Me5)RhCl}2(μ-Cl)2], gives rise to the cationic complexes, [(η5-C5Me5)RhCl(HL)]Cl (HL = HL1 (1), HL2 (2)), in which the cysteine ligand exhibits a κ2N,S coordination mode. In a basic medium, HL1 or HL2 reacts with [{(η5-C5Me5)RhCl}2(μ-Cl)2] to afford mixtures of two epimers at the metal centre of the neutral complexes, [(η5-C5Me5)RhCl(κ2N,O-L)] (HL = HL1 (3), HL2 (4)), in which amino carboxylate adopts a κ2N,O mode of coordination along with variable amounts of the cationic compounds, [(η5-C5Me5)Rh(κ3N,O,S-L)]Cl (HL = HL1 (6Cl), HL2 (7Cl)), which contain κ3N,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 κ2O,S coordinated derivative, [(η5-C5Me5)RhCl(κ2O,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 AgSbF6 to give the hexafluoroantimonates [(η5-C5Me5)Rh(κ3N,O,S-L)][SbF6] (HL = HL1 (6Sb), HL2 (7Sb), HL3 (8Sb)) with tridentate coordination. Compound 8Sb reacts with NaHCO3 to give the neutral complex [(η5-C5Me5)Rh(κ3N,O,S-L3–H)] (9), which can also be prepared by reacting the dimer [{(η5-C5Me5)RhCl}2(μ-Cl)2] with HL3 in the presence of two equivalents of NaHCO3. 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 [(η5-C5Me5)RhCl(κ2O,S-L3)] (5), [(η5-C5Me5)Rh(κ3N,O,S-L1)][SbF6] (6Sb), [(η5-C5Me5)Rh(κ3N,O,S-L2)][SbF6] (7Sb) and [(η5-C5Me5)Rh(κ3N,O,S-L3–H)] (9). Variable temperature 1H NMR studies reveal the existence of epimerization processes and theoretical calculations were used to discriminate their nature.
000061914 536__ $$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-40855-R$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53033-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-32095$$9info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2006-0015$$9info:eu-repo/grantAgreement/ES/MICINN/RYC-2013-13800
000061914 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000061914 590__ $$a4.029$$b2016
000061914 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2016$$dQ1$$eT1
000061914 592__ $$a1.229$$b2016
000061914 593__ $$aInorganic Chemistry$$c2016$$dQ1
000061914 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000061914 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez R.$$uUniversidad de Zaragoza
000061914 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F.J.$$uUniversidad de Zaragoza
000061914 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, P.$$uUniversidad de Zaragoza
000061914 700__ $$0(orcid)0000-0001-9801-2381$$aOsante, I.
000061914 700__ $$0(orcid)0000-0003-3222-0828$$aCativiela, C.$$uUniversidad de Zaragoza
000061914 700__ $$0(orcid)0000-0003-4500-1974$$aLópez, J.A.$$uUniversidad de Zaragoza
000061914 700__ $$aCarmona, D.
000061914 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000061914 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000061914 773__ $$g45, 36 (2016), 14203-14215$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000061914 8564_ $$s392863$$uhttps://zaguan.unizar.es/record/61914/files/texto_completo.pdf$$yPostprint
000061914 8564_ $$s70102$$uhttps://zaguan.unizar.es/record/61914/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000061914 909CO $$ooai:zaguan.unizar.es:61914$$particulos$$pdriver
000061914 951__ $$a2023-10-27-12:52:45
000061914 980__ $$aARTICLE