Russian Chemical Bulletin

, Volume 43, Issue 8, pp 1328–1331 | Cite as

A new nuclear spin selective reaction of molecular oxygen

  • A. L. Buchachenko
  • L. L. Yasina
  • A. L. Vdovina
  • A. B. Blyumenfel'd
Physical Chemistry
Received:

Abstract

During high-temperature (623–673 K) oxidation of polyarylenes (polypyromellitimide and polyphenylquinoxaline), the molecular oxygen is enriched in the18O nonmagnetic isotope and impoverished in the17O magnetic isotope. The isotope selection increases with the increase in the degree of conversion of oxygen. The spin-selective reaction responsible for the selection of the17O isotope is the addition of molecular oxygen to triplet exited aromatic fragments of macromolecules to give endoperoxides. This reaction, which is selective in terms of the electron spin, is also nuclear-spin selective resulting in a magnetic isotope effect. The selection of nonmagnetic isotopes,16O and18O, is caused by competition between the reversible and irreversible decomposition of endoperoxide and by the classical isotope effect in these reactions.

Key words

magnetic isotope effect isotope selection molecular oxygen oxygen isotopes oxidation of polyarylenes polypyromellitimide polyphenylquinoxaline 
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References

  1. 1.
    V. A. Belyakov, V. I. Mal'tsev, E. M. Galimov, and A. L. Buchachenko,Dokl. Akad. Nauk SSSR, 1978,243, 924 [Dokl. Chem., 1978,243 (Engl. Transl.)].Google Scholar
  2. 2.
    A. L. Buchachenko, A. V. Fedorov, L. L. Yasina, and E. M. Galimov,Chem. Phys. Lett., 1984,103, 405.Google Scholar
  3. 3.
    N. J. Turro and M. F. Chow,J. Am. Chem. Soc., 1980,102, 1190.Google Scholar
  4. 4.
    L. L. Yasina and A. L. Buchachenko,Chem. Phys., 1990,146, 225.Google Scholar
  5. 5.
    A. L. Buchachenko, E. M. Galimov, V. V. Ershov,Dokl. Akad. Nauk SSSR, 1976,228, 379 [Dokl. Chem., 1976,228 (Engl. Transl)].Google Scholar
  6. 6.
    A. L. Buchachenko,Progress in Reaction Kinetics, 1984,13, 163.Google Scholar
  7. 7.
    J. M. Angel,J. Pol. Sci., 1972,A1, 10, 2403.Google Scholar
  8. 8.
    B. M. Kovarskaya, N. G. Annenkova, V. V. Gur'yanova, and A. B. Blyumenfel'd,Vysokomolek. Soed. A, 1973,15, 2458 [Polym. Sci. USSR, 1973,15 (Engl. Transl.)].Google Scholar
  9. 9.
    A. B. Blyumenfel'd, A. L. Vdovina, A. P. Pleshkova, and N. G. Annenkova,Vysokomolek. Soed. B, 1986,28, 500 [Polym. Sci. USSR, 1986,28 (Engl. Transl.)].Google Scholar
  10. 10.
    B. M. Kovarskaya, N. G. Annenkova, V. V. Gur'yanova, and A. B. Blyumenfel'd,Vysokomolek. Soed. A, 1973,15, 2458 [Polym. Sci. USSR, 1986,28 (Engl. Transl.)].Google Scholar
  11. 11.
    A. L. Vdovina, Ph. D. (Chem.) Thesis, Int Plastmass, Moscow, 1988.Google Scholar
  12. 12.
    M. V. Bazilevskii,Metod molekulyarnykh orbitalei i reaktsionnaya sposobnost' organicheskikh molekul [Molecular Orbitals Method and Reactivity of Organic Molecules], Khimiya, Moscow, 1969, 303 (in Russian).Google Scholar
  13. 13.
    A. L. Vdovina, V. M. Ryaboi, and A. B. Blyumenfel'd,Vysokomolek. Soed. A, 1985,27, 808 [Polym. Sci. USSR, 1985,27 (Engl. Transl.)].Google Scholar

Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • A. L. Buchachenko
    • 1
  • L. L. Yasina
    • 1
  • A. L. Vdovina
    • 1
  • A. B. Blyumenfel'd
    • 1
  1. 1.N. N. Semenov Institute of Chemical PhysicsRussian Academy of SciencesMoscowRussian Federation

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