000096237 001__ 96237
000096237 005__ 20201119130017.0
000096237 0247_ $$2doi$$a10.1016/j.jorganchem.2015.09.039
000096237 0248_ $$2sideral$$a94000
000096237 037__ $$aART-2016-94000
000096237 041__ $$aeng
000096237 100__ $$0(orcid)0000-0003-1707-3022$$aCasado, M. A.$$uUniversidad de Zaragoza
000096237 245__ $$aReactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clusters
000096237 260__ $$c2016
000096237 5060_ $$aAccess copy available to the general public$$fUnrestricted
000096237 5203_ $$aTreatment of heterobimetallic sulfido-bridged complexes Cp(acac)Ti(µ3-S)2(M(cod))2] (M = Rh (1), Ir (2)) with the organic acids CX3COOH (X = F, H) forms the corresponding acetate derivatives Cp(CX3COO)Ti(µ3-S)2(M(cod))2] (X = F, M = Rh (3), Ir (4); X = H, M = Rh (5), M = Ir (6)). While complex 3 was easily isolated, compounds 4-6 establish in solution the corresponding equilibria with the starting complexes 1 and 2. Treatment of 1 with a hydrochloric acid solution in THF generates the heterohexanuclear cationic cluster (CpTi(µ3-S)2(Rh(cod))2)2(µ-OH)]Cl] (7), which is deprotonated with weak bases affording the oxo derivative (CpTi(µ3-S)2(Rh(cod))2)2(µ2-O)] (8). Cluster 8, and the analogous with the ligand methylcyclopentadienyl ((CpMe)Ti(µ3-S)2(Rh(cod))2)2(µ2-O)] (9), can be synthesized from reaction of the respective complexes Cp2Ti(SH)2] and (CpMe)2Ti(SH)2] with the methoxo-bridged dinuclear complex (Rh(µ-OMe)(cod))2] in the presence of water. A preliminary study of the molecular structure of 9 confirmed the formation of an almost linear array of the "Ti-O-Ti" subunit, in which each titanium atom supports two "Rh(cod)" moieties through two sulfido bridges. Further, the heterotetranuclear cluster CpTi(µ3-S)3Ir3(µ2-CO)(CO)3(PMe3)3] (10) reacts with alkynes at the triiridium metallic triangle. The reactions with activated alkynes, such as dimethyl acetylenedicarboxylate (or diethyl acetylenedicarboxylate) afford clusters CpTi(µ3-S)3Ir3(µ2-¿1-RO2CCCCO2R)(C(O)RO2CCCCO2R)(CO)3(PMe3)3] (R = Me (11), Et (12)), which incorporate two molecules of alkyne. The X-ray molecular structure of 11 shows that one alkyne is cis-metallated to the metal-metal bonded iridium centres whereas the other is taking part of a iridacyclobutenone moiety resulting from the CO migratory insertion into a iridium-alkyne bond at the third iridium centre. However, reaction of 10 with phenylacetylene stops at the cluster CpTi(µ3-S)3Ir3(µ2-¿1-PhCCH)(CO)3(PMe3)3] (13), which contains only a cis-metallated olefin to two metal-metal bonded iridium atoms. The X-ray molecular structure of CpTi(µ3-S)3Ir3(µ2-¿1-PhCCH)(H)(CO)3(PMe3)3]BF4] (14), the product resulting from protonation of 13 with HBF4·OEt2 shows that the TiIr3] core remains intact and that the olefin is indeed cis-metallated to the two metal-metal bonded iridium atoms, while the third iridium atom from the metallic triangle becomes protonated.
000096237 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E07$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E70$$9info:eu-repo/grantAgreement/ES/MICINN/CSD2009-00050$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2011-22516$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2012-35665$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P
000096237 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000096237 590__ $$a2.184$$b2016
000096237 591__ $$aCHEMISTRY, ORGANIC$$b27 / 59 = 0.458$$c2016$$dQ2$$eT2
000096237 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b17 / 46 = 0.37$$c2016$$dQ2$$eT2
000096237 592__ $$a0.647$$b2016
000096237 593__ $$aMaterials Chemistry$$c2016$$dQ2
000096237 593__ $$aInorganic Chemistry$$c2016$$dQ2
000096237 593__ $$aPhysical and Theoretical Chemistry$$c2016$$dQ2
000096237 593__ $$aOrganic Chemistry$$c2016$$dQ2
000096237 593__ $$aBiochemistry$$c2016$$dQ3
000096237 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000096237 700__ $$0(orcid)0000-0002-7188-8014$$aCiriano, M. A.
000096237 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F. J.$$uUniversidad de Zaragoza
000096237 700__ $$0(orcid)0000-0001-7154-7239$$aOro, L. A.$$uUniversidad de Zaragoza
000096237 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J. J.$$uUniversidad de Zaragoza
000096237 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000096237 773__ $$g812 (2016), 123-134$$pJ. organomet. chem.$$tJournal of Organometallic Chemistry$$x0022-328X
000096237 8564_ $$s375840$$uhttps://zaguan.unizar.es/record/96237/files/texto_completo.pdf$$yPostprint
000096237 8564_ $$s185636$$uhttps://zaguan.unizar.es/record/96237/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
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000096237 951__ $$a2020-11-19-11:45:42
000096237 980__ $$aARTICLE