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Kinetics and Catalysis

, Volume 46, Issue 1, pp 65–71 | Cite as

Catalysis of carbon tetrachloride conversion by copper complexes with monoethanolamine immobilized on the surface of silica

  • V. V. Smirnov
  • I. G. Tarkhanova
  • A. I. Kokorin
  • V. I. Pergushov
  • D. S. Tsvetkov
Article
  • 28 Downloads

Abstract

The catalytic properties of silica-immobilized copper complexes with monoethanolamine in reactions of CCl4 addition to 1-octene and combined metathesis of C-Cl and C-H bonds in the CCl4-decane system were studied. The catalytic activity was found to be an extremal function of metal concentration. The increase of activity during the addition of CCl4 to octene as the metal content was decreased to ~0.3 wt % can be explained by an increase in the fraction of mononuclear copper complexes of differing composition. Further changes in activity were due to the formation of metal complexes with various ligand environments. A comparison between EPR data and catalytic properties suggested that the most active catalysts contained a considerable number of divalent copper complexes with a coordination environment of four nitrogen atoms, which are more effective than oxygen at increasing electron density on copper ion; this facilitated the reduction of Cu(II) to Cu(I). The above complexes are unstable because the ligands are rigidly fixed on the surface and strained structures are formed. Ligands in the coordination sphere of the metal can be readily replaced by substrate molecules, which exhibit weak solvating power.

Keywords

CCl4 Catalytic Property Tetrachloride Carbon Tetrachloride Copper Complex 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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REFERENCES

  1. 1.
    Tarkhanova, I.G., and Rostovshchikova, T.N., Kine. Katal., 2001, vol. 42, no. 2, p.216.Google Scholar
  2. 2.
    Smirnov, V.V., Beletskaya, I.P., Levitskii, M.M., and Kazankova, M.A., Mendeleev Comun., 2000, p. 175.Google Scholar
  3. 3.
    RF Patent 2107678, 1998.Google Scholar
  4. 4.
    Smirnov, V.V., Tarkhanova, I.G., Zavin, B.G., and Bilyachenko, A.N., Kinet. Katal., 2003, vol. 44, no. 4, p. 625.Google Scholar
  5. 5.
    Smirnov, V.V., and Tarkhanova, I.G., Ross. Khim. Zh., 2001, vol. 45, no. 4, p. 75.Google Scholar
  6. 6.
    Golubeva, E.N., Smirnov, V.V., Vorontsov, P.I., and Koval’skii, D.A., Kinet. Katal., 1998, vol. 39, no. 6, p. 908.Google Scholar
  7. 7.
    Kokorin, A.I., Kirsh, Yu. E., and Zamaraev, K.I., Dokl. Akad. Nauk SSSR, 1972, vol. 202, no. 3, p. 597.Google Scholar
  8. 8.
    Chuiko, E.A., and Tertykh, V.A., Ukr. Khim. Zh., 1971, vol. 37, no. 1, p. 35.Google Scholar
  9. 9.
    Bertrand, A., and Van der Veer, D.G., Inorg. Chem., 1980, vol. 19, no. 7, p. 2022.Google Scholar
  10. 10.
    Bland, W.J., and Durrant, J.L.A., J. Organomet. Chem., 1985, vol. 280, p. 397.Google Scholar
  11. 11.
    Kokorin, A.I., Ser. Khim., 1997, no. 10, p. 1824.Google Scholar
  12. 12.
    Kopylova, V.D. and Astanina, A.N., Ionitnye kompleksy v katalize (Ion-Exchanger Complexes in Catalysis), Moscow: Khimiya, 1987.Google Scholar
  13. 13.
    Saraev, V.V. and Shmidt, F.K., EPR metallokompleksnykh katalizatorov (EPR of Metal Complex Catalysts), Irkutsk: Irkutsk. Gos. Univ., 1985.Google Scholar
  14. 14.
    Goodman, B.A. and Raynor, J.B., Adv. Inorg. Chem. Radiochem., 1970, vol. 13, p. 135.Google Scholar
  15. 15.
    Zamaraev, K.I., and Salikhov, K.M., Spinovyi obmen (Spin Exchange), Novosibirsk: Nauka, 1977.Google Scholar
  16. 16.
    Poznyak, S.K., Kokorin, A.I., Kulak, A.I., and Schlaepfer, C.W., J. Phys. Chem., 1999, vol. 103, p. 1308.Google Scholar
  17. 17.
    Kokorin, A.I., and Arutyunyan, V.M., Izv. Akad. Nauk, Ser. Khim., 2000, no. 1, p. 88.Google Scholar
  18. 18.
    Dembo, A.T., Volkov, V.V., et al., Langmuir, 2003, vol. 19, no. 19, p. 7845.Google Scholar
  19. 19.
    Kabanov, N.M., Rogacheva, V.B., and Zezin, A.B., Vysokomol. Soedinen., Ser. A, 1979, vol. 21, no. 1, p. 209.Google Scholar
  20. 20.
    Molochnikov, L.S. and Radionov, B.K., and Kokorin, A.I., J. Mol. Catal. A: Chem., 1998, vol. 129, no. 1/2, p. 141.Google Scholar
  21. 22.
    Kharitonov, D.N., Pergushov, V.I., Kokorin, A.I., and Smirnov, V.V., Kinet. Katal., 2001,vol. 42, no. 5, p. 741.Google Scholar
  22. 23.
    Kharitonov, D.N., 2003.Google Scholar
  23. 24.
    Asscher, M. and Vofsi, D., Velichko, F.K., and Terent’ev, A.B., Usp. Khim., 1984, vol. 53, no. 3, p. 370.Google Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2005

Authors and Affiliations

  • V. V. Smirnov
    • 1
  • I. G. Tarkhanova
    • 1
  • A. I. Kokorin
    • 1
  • V. I. Pergushov
    • 1
  • D. S. Tsvetkov
    • 1
  1. 1.Department of ChemistryMoscow State UniversityMoscowRussia

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