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Structure and Reactivity of the Radical Cations of Methyl tert-Butyl Ether in Condensed Phase: An ESR and Quantum Chemical Study

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Abstract

The structure of the methyl tert-butyl ether (MTBE) radical cation and mechanism of its thermal and photochemical reactions in irradiated freons (CFCl3, CF2ClCFCl2, and CF3CCl3) were studied. Radical products of MTBE radiolysis in the liquid phase were investigated by the spin trapping technique. The quantum-chemical calculations of the structure of MTBE radical cations and products of their transformations were carried out by density functional theory (DFT) and ab initioMP2 methods. The primary MTBE radical cations are stabilized in dilute solutions in CFCl3and CF3CCl3. The ion–molecule reaction (proton transfer from the radical cation) was found to occur in concentrated solutions in CFCl3immediately during irradiation. The action of light (λ = 436 to 546 nm) at 77 K on the MTBE radical cation in CFCl3and CF3CCl3matrices results in intramolecular migration of the methyl group to yield the distonic radical cation (CH3)2 .CO+(CH3)2. The primary MTBE radical cations undergo an irreversible transformation with methane elimination resulting in formation of the 2-methoxypropene radical cation .CH2=С+(СН3)ОСН3in CFCl3and CF3CCl3matrices in the temperature range 110–130 K. In the case of CF2ClCFCl2matrix, such a reaction occurs during irradiation at 77 K. Using the spin trapping technique, it was shown that the liquid-phase radiolysis of the neat ether resulted in the formation of fragmentation products (.CH3,CH3О., and t-BuO. radicals) from the primary radical cations, as well as the products of their rearrangements and ion–molecule reactions.

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REFERENCES

  1. Fangstrom, T.,Lunell, S.,Engels, B.,Ericsson, L.A.,Shiotani, M., andKomaguchi, K., J. Chem. Phys., 1997, vol. 107, no. 2, p. 297.

    Article  Google Scholar 

  2. Belevskii, V.N.,Belopushkin, S.I.,Tyurin, D.A., andChuvylkin, N.D., Khim. Vys. Energ., 1999, vol. 33, no. 2, p. 104 [High Energy Chem. (Engl. transl.), 1999, vol. 33, no. 2, p. 77].

    Google Scholar 

  3. Shchapin, I.Yu.,Feldman, V.I.,Belevskii, V.N.,Don-skaya, N.A., andChuvylkin, N.D., Izv. Akad. Nauk, Ser. Khim., 1995, no. 2, p. 212.

  4. Symons, M.C.R., Chem. Soc. Rev., 1984, no. 4, p. 313.

  5. Radical Ionic Systems. Properties in Condensed Phases, Lund, A. andShiotani, M., Eds., Dordrecht: Kluwer, 1991.

    Google Scholar 

  6. Feldman, V.I., Acta Chem. Scand., 1997, vol. 51, no. 2, p. 181.

    Google Scholar 

  7. Belevskii, V.N. andBelopushkin, S.I., Dokl. Akad. Nauk SSSR, 1990, vol. 310, no. 5, p. 1138.

    Google Scholar 

  8. Belevskii, V.N.,Belopushkin, S.I., andFeldman, V.I., Khim. Vys. Energ., 1988, vol. 22, no. 2, p. 118.

    Google Scholar 

  9. Belevskii, V.N.,Belopushkin, S.I.,Baranova, I.A., andTyurin, D.A., Khim. Vys. Energ., 1999, vol. 33, no. 6, p. 433 [High Energy Chem. (Engl. transl.), 1999, vol. 33, no. 6, p. 379].

    Google Scholar 

  10. Symons, M.C.R. andWren, B.W., J. Chem. Soc. Perkin Trans. 2, 1984, no. 3, p. 511.

  11. Becker, H. et al., Organikum: Practical Handbook of Organic Chemistry, Oxford: Pergamon, 1973. Translated under the title Organikum (Praktikum po organicheskoi khimii), Moscow: Mir, 1992.

    Google Scholar 

  12. Tyurin, D.A.,Mel'nikov, M.Ya., andBelevskii, V.N., Khim. Vys. Energ., 2001, vol. 35, no. 4, p. 266 [High Energy Chem. (Engl. transl.), 2001, vol. 35, no. 4, p. 236].

    Google Scholar 

  13. Laikov, D.N., Chem. Phys. Lett., 1997, vol. 281, no. 1-3, p. 151.

    Article  Google Scholar 

  14. Perdew, J.P.,Burke, K., andErnzerhof, M., Phys. Rev. Lett., 1996, vol. 77, no. 18, p. 3865.

    Article  Google Scholar 

  15. Laikov, D.N., Cand. Sc. (Phys.-Math.) Dissertation, Moscow: Moscow State Univ., 2000.

    Google Scholar 

  16. Dunning, T.H., Jr., J. Chem. Phys., 1989, vol. 90, p. 1007.

    Article  Google Scholar 

  17. Melnikov, M.Ya.,Baskakov, D.V.,Baranova, I.A., andBelevskii, V.N., Mendeleev Commun., 1998, no. 1, p. 2.

  18. Bowen, R.D. andMaccoll, A., J. Chem. Soc. Perkin Trans. 2, 1990, no. 1, p. 147.

  19. Becker, D.,Swarts, S., andSevilla, M.D., J. Phys. Chem., 1985, vol. 89, no. 12, p. 2638.

    Google Scholar 

  20. Knolle, W.,Janovskii, I.,Naumov, S., andMehnert, R., Radiat. Phys. Chem., 1999, vol. 55, nos. 5-6, p. 625

    Article  Google Scholar 

  21. Fridgen, T.D. andParnis, J.M., Int. J. Mass Spectrom. Ion Processes, 1999, vols. 190/191, p. 181.

    Google Scholar 

  22. Zubarev, V.E.,Belevskii, V.N., andBugaenko, L.T., Vestn. Mosk. Univ., Ser.: Khim., 1975, vol. 16, no. 3, p. 295.

    Google Scholar 

  23. Oto, N.,Niki, E., andKamiya, Y., J. Chem. Soc. Perkin Trans. 2, 1977, no. 13, 1770.

  24. Belevskii, V.N., Khim. Vys. Energ., 1981, vol. 15, no. 1, p. 3.

    Google Scholar 

  25. Yarkov, S.P.,Belevskii, V.N.,Zubarev, V.E., andBugaenko, L.T., Khim. Vys. Energ., 1978, vol. 12, no. 2, p. 131.

    Google Scholar 

  26. Terabe, S. andKonake, R., J. Chem. Soc. Perkin Trans. 2, 1973, p. 369.

    Google Scholar 

  27. Mel'nikov, M.Ya.,Mel'nikova, O.L.,Belevskii, V.N., andBelopushkin, S.I., Khim. Vys. Energ., 1998, vol. 32, no. 1, p. 39 [High Energy Chem. (Engl. transl.), 1998, vol. 32, no. 1, p. 34].

    Google Scholar 

  28. Levin, R.D. andLias, S.G., Ionization Potential and Appearance Potential Measurements, Washington, DC National Bureau of Standards, 1971-1981, Natl. Stand. Ref. Data Ser., no. 71.

    Google Scholar 

  29. Belevskii, V.N.,Belopushkin, S.I., andFeldman, V.I., Dokl. Akad. Nauk SSSR, 1990, vol. 310, no. 4, p. 897.

    Google Scholar 

  30. Knight, L.B.,Kerr, K.,Villanueva, M.,McKinley, A., andFeller, D, J. Chem. Phys., 1992, vol. 97, no. 8, p. 5363.

    Article  Google Scholar 

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  1. Moscow State University, Moscow, 119899, Russia

    D. A. Tyurin & V. N. Belevskii

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Tyurin, D.A., Belevskii, V.N. Structure and Reactivity of the Radical Cations of Methyl tert-Butyl Ether in Condensed Phase: An ESR and Quantum Chemical Study. High Energy Chemistry 35, 404–416 (2001). https://doi.org/10.1023/A:1012534725443

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