title: Synthesis of Ir(III) complexes with Tp(Me2) and acac ligands and their reactivity with electrophiles.
abstract: The reaction of the bis(ethylene) complex [Tp(Me2)Ir(C2H4)2] () (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate) with an excess of 2,4-pentanedione (acetylacetone, Hacac) at 70 °C produced a mixture of the Ir(iii) complex [Tp(Me2)Ir(acac)(C2H5)] () as a major product (67% yield) and two other side complexes [Tp(Me2)Ir(acac)(H)] () and [Tp(Me2)Ir(C9H14O2)] () in 20 and 13% yields, respectively. According to the proposed reaction mechanism and DFT calculations, complexes and are generated from an 18e(-) intermediate [Tp(Me2)Ir(C2H4)(acac)(C2H3)] () which undergoes either hydrogen insertion or β-hydride elimination followed by the subsequent loss of a molecule of ethylene. The lowest yielding complex which features a 2-iridafuran is presumably generated from an unusual thermal coupling between one vinylic and one acac moiety. The availability of the acidic α-proton of the acac ligand was tested by the treatment of complex with Br2 and Cu(NO3)2 rendering the substitution complexes [Tp(3-Br,Me2)Ir(3-Br-acac)Br] () and [Tp(Me2)Ir(3-NO2-acac)(C2H5)] () in good yields. The series of heteroleptic iridium(iii) compounds display air and moisture stability and have been characterized by NMR, IR, and elemental analyses, and, in the case of , and , by single-crystal X-ray diffraction analyses.
authors.affiliation: Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca-Tulancingo Km. 4.5, Mineral de la Reforma, Hidalgo, 42090, México. salazar@correo.azc.uam.mx.
authors.forename: Judith P
authors.initials: JP
authors.lastname: Morales-Cerón
authors.forename: Verónica
authors.initials: V
authors.lastname: Salazar-Pereda
authors.forename: Daniel
authors.initials: D
authors.lastname: Mendoza-Espinosa
authors.forename: José G
authors.initials: JG
authors.lastname: Alvarado-Rodríguez
authors.forename: Julián
authors.initials: J
authors.lastname: Cruz-Borbolla
authors.forename: Noemí
authors.initials: N
authors.lastname: Andrade-López
authors.forename: José M
authors.initials: JM
authors.lastname: Vásquez-Pérez