doi:10.1016/j.jorganchem.2015.09.039engCasado, M. A.Ciriano, M. A.Lahoz, F. J.Oro, L. A.Pérez-Torrente, J. J.Reactivity of [TiM2] (M = Rh, Ir) and [TiIr3] early-late heterobimetallic sulfido-bridged clustersART-2016-94000Treatment 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.2016http://zaguan.unizar.es/record/9623710.1016/j.jorganchem.2015.09.039http://zaguan.unizar.es/record/96237oai:zaguan.unizar.es:96237info:eu-repo/grantAgreement/ES/DGA-FSE/E07info:eu-repo/grantAgreement/ES/DGA-FSE/E70info:eu-repo/grantAgreement/ES/MICINN/CSD2009-00050info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2011-22516info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2012-35665info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-PJournal of Organometallic Chemistry 812 (2016), 123-134All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess