Počet záznamů: 1

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

  1. 1.
    0342383 - UFCH-W 2011 RIV CH eng J - Článek v odborném periodiku
    Kaim, A. - Sieger, M. - Greulich, S. - Sarkar, B. - Fiedler, Jan - Záliš, Stanislav
    The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure.
    Journal of Organometallic Chemistry. Roč. 695, č. 7 (2010), s. 1052-1058 ISSN 0022-328X
    Grant CEP: GA AV ČR KAN100400702; GA MŠk OC 139; GA MŠk OC09043
    Výzkumný záměr: CEZ:AV0Z40400503
    Klíčová slova: 1,4-diazabutadiene * electronic structure * iridium compounds
    Kód oboru RIV: CG - Elektrochemie
    Impakt faktor: 2.205, rok: 2010

    Oxidation of the unambiguously characterized iridium(III)-enediamido complex IrCp*(RNCHCHNR), R = 2,6-dimethylphenyl, with six cyclically arranged p electrons was investigated using EPR and UV-vis spectroelectrochemistry. In contrast to a corresponding iminocatecholato system reported recently by Rauchfuss et al. [27] the two one-electron oxidation steps are not completely reversible, depending on the solvent. We attribute the electrochemical behavior observed in weakly coordinating dichloromethane and propylene carbonate solvents to an enhanced propensity for ligand addition: while neutral IrCp*(RNCHCHNR) remains coordinatively unsaturated with the strongly sigma and pi donating enediamido(2-) ligand mitigating the electron deficit, the oxidation to the less donating radical anion ligand (RNCHCHNR)(center dot-) or even to neutral 1,4-diazabutadiene is considered to induce a strong tendency for quasi-hexacoordination in [IrCp*(L)(RNCHCHNR)], L = solvent, halide, substrate.
    Trvalý link: http://hdl.handle.net/11104/0185131