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ESR Studies of the Oxidation Mechanism of Pyrazine-di-N-oxides in the Presence of Methanol and its Deuterated Derivativesстатья
- Авторы: Kulakovskaya S.I., Kulikov A.V., Shestakov A.F.
- Журнал: Russian Journal of Electrochemistry
- Том: 48
- Год издания: 2012
- Издательство: Maik Nauka/Interperiodica Publishing
- Местоположение издательства: Russian Federation
- Первая страница: 1023
- Последняя страница: 1036
- Аннотация: The mechanism of oxidation of pyrazine-, 2,5-di-Me-, and 2,3,5,6-tetra-Me-pyrazine-di-N-oxides in the presence of methanol and its deuterated derivatives (CH3OD, CD3OD), i.e., compounds exhibiting the high energy of C–H bond dissociation, is studied by the methods of cyclic voltammetry, EPR electrolysis, and quantum chemical modeling. The study is carried out on a glassy carbon (GC) electrode in acetonitrile and on an Au electrode in solutions of different alcohols (methanol and its deuterated derivativesCH3OD, CD3OD). In alcohol solutions, the EPR spectra of radical cations and radical anions of the tested aromatic di-N-oxides are observed. The quantum chemical simulation of the reaction of the pyrazine-di-N-oxide radical cation with the MeOH C–H bond is carried out. The results obtained are explained within the framework of the E1C1E2C2 mechanism for a two-stage electrode process determined by the catalytic currenton the second electrode stage. The overall two-electron catalytic oxidation of an alcohol within its complex with the pyrazine-di-N-oxide radical cation is proposed.
- Добавил в систему: Kulakovskaya Svetlana Ivanovna