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Electrochemical and ESR studies of tert-butanol oxidation mechanism in the presence of radical cations pyrazine-di-N-oxide and its substituted derivatives as mediators

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Abstract

The methods of cyclic voltammetry, ESR electrolysis, and quantum chemical simulation were used to study the tert-butanol (tert-BuOH) oxidation mechanism in the presence of mediator cation radicals of pyrazine-di-N-oxide, 2,5-di-Me- and 2,3,5,6-tetra-Me-pyrazine-di-N-oxdides. This study was carried out on carbon glass (CG) and Pt electrodes in 0.1 M LiClO4 solution in acetonitrile and on Au electrode in tert-butanol containing 0.05 M LiClO4. The ESR spectra of cation and anion radicals of aromatic di-N-oxides were recorded in tert-BuOH. The quantum chemical simulation of the reaction between pyrazine-di-N-oxide radical cation and C-H bond in tert-BuOH was performed. The results were explained in the terms of the general two-electron oxidation mechanism of tert-BuOH in the complex with aromatic di-N-oxide cation radical as mediator.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region, 142432, Russia

    S. I. Kulakovskaya, A. V. Kulikov & A. F. Shestakov

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  1. S. I. Kulakovskaya
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  2. A. V. Kulikov
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  3. A. F. Shestakov
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Correspondence to S. I. Kulakovskaya.

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Original Russian Text © S.I. Kulakovskaya, A.V. Kulikov, A.F. Shestakov, 2010, published in Elektrokhimiya, 2010, Vol. 46, No. 9, pp. 1116–1124.

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Kulakovskaya, S.I., Kulikov, A.V. & Shestakov, A.F. Electrochemical and ESR studies of tert-butanol oxidation mechanism in the presence of radical cations pyrazine-di-N-oxide and its substituted derivatives as mediators. Russ J Electrochem 46, 1047–1055 (2010). https://doi.org/10.1134/S1023193510090119

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  • DOI: https://doi.org/10.1134/S1023193510090119

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