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Electrochemical and ESR studies of the oxidation mechanism of pyrazine-di-N-oxides in the presence of methanol and its deuterated derivatives

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Abstract

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, ESR 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 derivatives CH3OD, CD3OD). In alcohol solutions, the ESR 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 current of 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.

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References

  1. Kulakovskaya, S.I., Berdnikov, V.M., Tikhonov, A.Ya., Volodarskii, L.B., and Maier, V.E., Russ. J. Electrochem., 1993, vol. 29, p. 40.

    Google Scholar 

  2. Kulakovskaya, S.I., Berdnikov, V.M., Vasilenko, A.A., Tikhonov, A.Ya., and Volodarskii, L.B., Russ. J. Electrochem., 1996, vol. 32, p. 784.

    CAS  Google Scholar 

  3. Kulakovskaya, S.I., Kulikov, A.V., Berdnikov, V.M., Ioffe, N.T., and Shestakov, A.F., Electrochim. Acta, 2002, vol. 47, p. 4245.

    Article  CAS  Google Scholar 

  4. Kulakovskaya, S.I., Kulikov, A.V., and Shestakov, A.F., Russ. J. Electrochem., 2004, vol. 40, p. 1035.

    Article  CAS  Google Scholar 

  5. Kulakovskaya, S.I., Kulikov, A.V., and Shestakov, A.F., Russ. J. Electrochem., 2007, vol. 43, p. 1156.

    Article  CAS  Google Scholar 

  6. Kulakovskaya, S.I., Kulikov, A.V., and Shestakov, A.F., Russ. J. Electrochem., 2007, vol. 43, p. 1234.

    Article  CAS  Google Scholar 

  7. Kulakovskaya, S.I., Kulikov, A.V., and Shestakov, A.F., Russ. J. Electrochem., 2009, vol. 45, p. 1368.

    Article  CAS  Google Scholar 

  8. Kulakovskaya, S.I., Kulikov, A.V., and Shestakov, A.F., Russ. J. Electrochem., 2010, vol. 46, p. 1047.

    Article  CAS  Google Scholar 

  9. Kondrat’ev, V.N., in Energiya razryva khimicheskikh svyazei. Potentsial ionizatsii i srodstvo k elektronu (Chemical Bond Dissociation Energy, Ionization Potential and Electron Affinity), Moscow: Nauka, 1962.

    Google Scholar 

  10. Grigor’eva, K.N., Tikhonov, A.Ya., Amitina, S.A., Volodarskii, L.B., and Korobeinicheva, I.K., Khim. Geterotsikl. Soedin., 1986, no. 3, p. 331.

  11. Grigor’eva, K.N., Amitina, S.A., and Volodarskii, L.B., Khim. Geterotsikl. Soedin., 1983, no. 10, p. 1387.

  12. Volodarskii, L.B., Amitina, S.A., and Dulepova, N.V., Izv. Akad. Nauk SSSR, Ser. Khim., 1979, no. 4, p. 904.

  13. Nicholson, R.S. and Shain, J., Anal. Chem., 1964, vol. 36, p. 706.

    Article  CAS  Google Scholar 

  14. Nicholson, R.S. and Shain, J., Anal. Chem., 1965, vol. 37, p. 178.

    Article  CAS  Google Scholar 

  15. Nishikida, K., Kubota, T., Miyazaki, H., and Sakata, S., J. Magnetic Resonance, 1972, vol. 7, p. 260.

    CAS  Google Scholar 

  16. Denisov, E., in Handbook of Antioxidants. Bond Dissociation Energies, Rate Constants, Activation Energies and Enthalpies of Reactions, New York: CRC, 1995, p. 27.

    Google Scholar 

  17. Galus, Z., Teoretyczne Podstawy Electroanalizy Chemiczne, Warszawa: Panstwowe Wydawnictwo Naukowe, 1971 (translated into Russian).

    Google Scholar 

  18. Kubota, T. and Miyazaki, H., Bull. Chem. Soc. Jpn., 1962, vol. 35, p. 1549.

    Article  CAS  Google Scholar 

  19. Kubota, T. and Miyazaki, H., Bull. Chem. Soc. Jpn., 1970, vol. 43, p. 1622.

    Article  CAS  Google Scholar 

  20. Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865.

    Article  CAS  Google Scholar 

  21. Stevens, W.J., Basch, H., and Krauss, M.J., Chem. Phys., 1984, vol. 81, p. 6026.

    Google Scholar 

  22. Laikov, D.N. and Ustynyuk, Y.A., Russ. Chem. Bull, 2005, vol. 54, p. 820.

    Article  CAS  Google Scholar 

  23. Golubev, V.A., Miklyush, R.V., and Rozantsev, E.G., Izv. AN SSSP, Ser. Khim., 1972, no. 3, p. 656.

  24. Golubev, V.A. and Miklyush, R.V., Zh. Org. Khim., 1972, vol. 8, p. 1356.

    CAS  Google Scholar 

  25. Rontus, M. and Delmelic, M., CR Acad. Sci., Ser. D, 1973, vol. 227, p. 1069.

    Google Scholar 

  26. Katritzky, A.R., J. Chem. Soc., 1956, p. 2404.

  27. Okamoto, T. and Tani, H., Chem. Pharm. Bull., 1959, vol. 7, p. 130.

    Article  CAS  Google Scholar 

  28. Okamoto, T. and Tani, H., Chem. Pharm. Bull., 1959, vol. 7, p. 925.

    Article  Google Scholar 

  29. Katritzky, A.R. and Lunt, E., Tetrahedron, 1969, vol. 25, p. 4291.

    Article  CAS  Google Scholar 

  30. Eisenthal, R. and Katritzky, A.R., Tetrahedron, 1965, vol. 21, p. 2205.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, p/o Chernogolovka, Noginskii raion, Moskovskaya oblast’, 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, 2012, published in Elektrokhimiya, 2012, Vol. 48, No. 10, pp. 1123–1136.

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Kulakovskaya, S.I., Kulikov, A.V. & Shestakov, A.F. Electrochemical and ESR studies of the oxidation mechanism of pyrazine-di-N-oxides in the presence of methanol and its deuterated derivatives. Russ J Electrochem 48, 1023–1036 (2012). https://doi.org/10.1134/S1023193512040088

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  • DOI: https://doi.org/10.1134/S1023193512040088

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