Number of the records: 1  

Acceptor-Substituted Ferrocenium Salts as Strong, Single-Electron Oxidants: Synthesis, Electrochemistry, Theoretical Investigations, and Initial Synthetic Application

  1. 1.
    0384930 - ÚOCHB 2013 RIV DE eng J - Journal Article
    Khobragade, Dushant - Mahamulkar, Shraddha G. - Pospíšil, Lubomír - Císařová, I. - Rulíšek, Lubomír - Jahn, Ullrich
    Acceptor-Substituted Ferrocenium Salts as Strong, Single-Electron Oxidants: Synthesis, Electrochemistry, Theoretical Investigations, and Initial Synthetic Application.
    Chemistry - A European Journal. Roč. 18, č. 39 (2012), s. 12267-12277. ISSN 0947-6539. E-ISSN 1521-3765
    R&D Projects: GA ČR GA203/09/0705
    Institutional support: RVO:61388963
    Keywords : metallocenes * cyclic voltammetry * lactones * oxidation * redox chemistry
    Subject RIV: CC - Organic Chemistry
    Impact factor: 5.831, year: 2012

    A series of mono- and 1,1'-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1'-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030 V and the maximum deviation to 0.1 V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties.
    Permanent Link: http://hdl.handle.net/11104/0214386

     
     
Number of the records: 1  

  This site uses cookies to make them easier to browse. Learn more about how we use cookies.