Počet záznamů: 1

Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives

  1. 1.
    0361581 - UFCH-W 2012 RIV GB eng J - Článek v odborném periodiku
    Hoskovcová, I. - Zvěřinová, R. - Roháčová, J. - Dvořák, D. - Tobrman, T. - Záliš, Stanislav - Ludvík, Jiří
    Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives.
    Electrochimica acta. Roč. 56, č. 19 (2011), s. 6853-6859 ISSN 0013-4686
    Grant CEP: GA AV ČR IAA400400813
    Výzkumný záměr: CEZ:AV0Z40400503
    Klíčová slova: DFT calculations * electrochemistry * Fischer aminocarbene complexes
    Kód oboru RIV: CG - Elektrochemie
    Impakt faktor: 3.832, rok: 2011

    This contribution shows how a small change of a remote substituent (COOCH3 for e.g. OCH3) on Fischer aminocarbene complexes can change totally the LUMO location, and thus electron distribution, extent of π-electron delocalization and, consequently, redox properties of these potential catalysts. During investigation of redox properties of extended series of title compounds, an exceptionally positive reduction potential was observed (non fitting the LFER plot) for p-COOR substituents. This effect is caused by a strong intramolecular electronic interaction, which is specific for p-phenylene dicarbonyl compounds. In this context, the CN bond in aminocarbene moiety has a double bond character and resembles carbonyl function. The interpretation was proved by DFT calculations.
    Trvalý link: http://hdl.handle.net/11104/0198867