Počet záznamů: 1

Bis(acetylacetonato)ruthenium Complexes of Noninnocent 1,2-Dioxolene Ligands: Qualitatively Different Bonding in Relation to Monoimino and Diimino Analogues

  1. 1.
    SYSNO ASEP0369092
    Druh ASEPJ - Článek v odborném periodiku
    Zařazení RIVJ - Článek v odborném periodiku
    NázevBis(acetylacetonato)ruthenium Complexes of Noninnocent 1,2-Dioxolene Ligands: Qualitatively Different Bonding in Relation to Monoimino and Diimino Analogues
    Tvůrce(i)Das, D. (IN) - Sarkar, B. (DE) - Kumbhakar, D. (IN) - Mondal, T. P. (IN) - Mobin, S. M. (IN) - Fiedler, Jan (UFCH-W) - Urbanos, F. A. (ES) - Jimenez-Aparicio, R. (ES) - Kaim, W. (DE) - Lahiri, G. K. (IN)
    Rozsah stran11030 - 11040
    Zdroj.dok.Chemistry - A European Journal - ISSN 0947-6539
    Poč.str.9 s.
    Jazyk dok.eng - angličtina
    Země vyd.DE - Německo
    Klíč. slovadensity functional calculations ; magnetic properties ; ruthenium
    Vědní obor RIVCF - Fyzikální chemie a teoretická chemie
    CEPGA203/09/0705 GA ČR - Grantová agentura ČR
    LD11082 GA MŠk - Ministerstvo školství, mládeže a tělovýchovy
    CEZAV0Z40400503 - UFCH-W (2005-2011)
    UTISI000296262400032
    DOI10.1002/chem.201101009
    AnotaceCoordination compounds [Ru(acac)(2)(Q)] (acac = acetylacetonate; Q = o-benzoquinone) were prepared as complexes 1 (Q = o-benzoquinone), 2 (Q = 3-methoxy-o-benzoquinone), 3 (Q = 4-methyl-o-benzoquinone), and 4 (Q = 3,5-di-tert-butyl-o-benzoquinone). The structures of 1 and 2 were determined to reveal a Ru(III)/o-benzosemiquinone formulation, supported by analysis of experimental data (spectroscopy, magnetism of 1) and by DFT calculations. The S = 1 ground state calculated for 1 stands in contrast to the spin-paired analogues with arylimino-o-benzosemiquinonato and diimino-o-benzoquinone ligands. The close contacts of about 5.3 angstrom possible between semiquinone O atoms of different molecules in the crystal allow for intermolecular spin-spin interactions and an overall complex magnetic behavior. One quasireversible oxidation and two reversible one-electron reductions yielded the corresponding molecular ions, which were characterized by UV-visible-NIR and EPR spectroelectrochemistry in terms of [Ru(III)(acac)(2)(Q(0))](+), [Ru(III)(acac)(2)(Q(2-))](-), and [Ru(II)(acac)(2)(Q(2-))](2-) descriptions in agreement with DFT results.
    PracovištěÚstav fyzikální chemie J.Heyrovského
    KontaktMichaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
    Rok sběru2012