title: C-H Bond activation and C-C bond formation in the reaction of 2,5-dimethylthiophene with TpMe2Ir compounds.
abstract: The bulky 2,5-dimethylthiophene (2,5-Me2T) reacts at 60 degrees C with TpMe2Ir(C2H4)2 to give a mixture of two TpMe2Ir(III) hydride products, 3 and 4, that contain in addition a thienyl (3) or a thienyl-derived ligand (4). For the generation of 3 only sp2 C-H activation is needed, but the formation of 4 requires also the activation of an sp3 C-H bond and the formation of a new C-C bond (between vinyl and thienyl fragments). In the presence of 2,5-Me2T, compound 4 reacts further to produce a complex thiophenic structure (5, characterized by X-ray methods) that derives formally from two molecules of 2,5-Me2T and a vinyl fragment. Compounds 3-5 can be readily protonated by [H(OEt2)2][BAr'4](Ar'= 3,5-C6H3(CF3)2), with initial generation of carbene ligands (in the case of 3 and 5) as a consequence of H+ attack at the beta-carbon of the Ir-thienyl unit. Free, substituted thiophenes, derived from the original 2,5-Me2T, may be isolated in this way.
authors.affiliation: Instituto de Investigaciones Químicas-Departamento de Química Inorgánica, Consejo Superior de Investigaciones Cientificas-Universidad de Sevilla, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092, Sevilla, Spain. paneque@iiq.csic.es
authors.forename: Margarita
authors.initials: M
authors.lastname: Paneque
authors.forename: Manuel L
authors.initials: ML
authors.lastname: Poveda
authors.forename: Ernesto
authors.initials: E
authors.lastname: Carmona
authors.forename: Verónica
authors.initials: V
authors.lastname: Salazar