Počet záznamů: 1  

Low-Valent Cobalt Complexes with Three Different .pí. Acceptor Ligands: Experimental and DFT Studies of the Reduced and the Low-Lying Excited States of (R-DAB)Co(NO)(CO), R-DAB = Substituted 1,4-Diaza-1,4-butadiene

  1. 1.
    0181739 - UFCH-W 20030173 RIV US eng J - Článek v odborném periodiku
    Sieger, M. - Wanner, M. - Kaim, W. - Stufkens, D. J. - Snoeck, T. - Záliš, Stanislav
    Low-Valent Cobalt Complexes with Three Different .pí. Acceptor Ligands: Experimental and DFT Studies of the Reduced and the Low-Lying Excited States of (R-DAB)Co(NO)(CO), R-DAB = Substituted 1,4-Diaza-1,4-butadiene.
    Inorganic Chemistry. Roč. 42, - (2003), s. 3340-3346. ISSN 0020-1669. E-ISSN 1520-510X
    Grant CEP: GA MŠMT OC D14.20
    Výzkumný záměr: CEZ:AV0Z4040901
    Klíčová slova: cobalt * experimental and DFT studies * substituted 1,4-diaza-1,4-butadiene
    Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
    Impakt faktor: 3.389, rok: 2003

    The complexes (RN=CH-CH=NR)Co(NO)(CO) with R = isopropyl, 2,6-diisopropylphenyl or p-tolyl are chemically and electrochemically reducible to radical anions at potentials strongly dependent on R. The DFT calculated structure for the neutral compound with R = iPr agrees with the experiment and the computed structure of the anion radical reveals changes according to a reduction of the R-DAB ligand. EPR results confirm an (R-DAB)-based singly occupied molecular orbital in [(RNCHCHNR)Co(NO)(CO)]-, with minor but detectable contributions from NO as supported by IR spectroelectrochemistry and as quantified by DFT spin density calculations. The calculations indicate increasingly stabilized CO, NO and RNCHCHNR * acceptor orbitals, in that order. Based on TD-DFT calculations, the lowest-lying excited states are assigned to metal-to-(R-DAB) charge transfer transitions while bands due to the metal-to-nitrosyl charge transfer occur at higher energies but still in the region.
    Trvalý link: http://hdl.handle.net/11104/0001933

     
     

Počet záznamů: 1  

  Tyto stránky využívají soubory cookies, které usnadňují jejich prohlížení. Další informace o tom jak používáme cookies.