96237 20201119130017.0 doi 10.1016/j.jorganchem.2015.09.039 sideral 94000 ART-2016-94000 eng (orcid)0000-0003-1707-3022 Casado, M. A. Universidad de Zaragoza Reactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clusters 2016 Access copy available to the general public Unrestricted Treatment 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. info:eu-repo/grantAgreement/ES/DGA-FSE/E07 info:eu-repo/grantAgreement/ES/DGA-FSE/E70 info:eu-repo/grantAgreement/ES/MICINN/CSD2009-00050 info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2011-22516 info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2012-35665 info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 2.184 2016 CHEMISTRY, ORGANIC 27 / 59 = 0.458 2016 Q2 T2 CHEMISTRY, INORGANIC & NUCLEAR 17 / 46 = 0.37 2016 Q2 T2 0.647 2016 Materials Chemistry 2016 Q2 Inorganic Chemistry 2016 Q2 Physical and Theoretical Chemistry 2016 Q2 Organic Chemistry 2016 Q2 Biochemistry 2016 Q3 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion (orcid)0000-0002-7188-8014 Ciriano, M. A. (orcid)0000-0001-8054-2237 Lahoz, F. J. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Oro, L. A. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Pérez-Torrente, J. J. Universidad de Zaragoza 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 812 (2016), 123-134 J. organomet. chem. Journal of Organometallic Chemistry 0022-328X 375840 http://zaguan.unizar.es/record/96237/files/texto_completo.pdf Postprint 185636 http://zaguan.unizar.es/record/96237/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:96237 articulos driver 2020-11-19-11:45:42 ARTICLE