Russian Journal of Organic Chemistry

, Volume 43, Issue 7, pp 970–980 | Cite as

Density functional study on the bromination of heteroelement-substituted acetylenes

  • M. V. Zabalov
  • S. S. Karlov
  • D. A. Lemenovskii
  • G. S. Zaitseva


The reactions of heteroelement-containing alkynes H3SiC≡CH and R3MC≡CPh [R3M = H3Si, Et3Si, Et3Ge, (MeO)3Si, (EtO)3Ge, N(CH2CH2O)3Si, N(CH2CH2O)3Ge, Bu3Sn] with one and two bromine molecules were studied in terms of the density functional theory. Transition states along reaction channels leading to products of both addition at the triple bond (cis- and trans-dibromoalkenes and 1,1-dibromoalkenes) and cleavage of the M-C≡ bond were localized.


Transition State Alkyne Bromine Triple Bond Germyl 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Ruasse, M.-F., Adv. Phys. Org. Chem., 1993, vol. 28, p. 207.CrossRefGoogle Scholar
  2. 2.
    Melloni, G., Modena, G., and Tonellato, U., Acc. Chem. Res., 1981, vol. 14, p. 227.CrossRefGoogle Scholar
  3. 3.
    Lenoir, D. and Chiappe, C., Chem. Eur. J., 2003, vol. 9, p. 1036.CrossRefGoogle Scholar
  4. 4.
    Pincock, J.A. and Yates, K., J. Am. Chem. Soc., 1968, vol. 90, p. 5643.CrossRefGoogle Scholar
  5. 5.
    Pincock, J.A. and Yates, K., Can. J. Chem., 1970, vol. 48, p. 3332.CrossRefGoogle Scholar
  6. 6.
    Schmid, G.H., Modro, A., and Yates, K., J. Org. Chem., 1980, vol. 45, p. 665.CrossRefGoogle Scholar
  7. 7.
    Yates, K., Schmid, G.H., Regulski, T.W., Garratt, D.G., Leung, H.W., and McDonald, R., J. Am. Chem. Soc., 1973, vol. 95, p. 160.CrossRefGoogle Scholar
  8. 8.
    Uemura, S., Okazaki, H., Okano, M., Sawada, S., Okada, A., and Kuwabara, K., Bull. Chem. Soc. Jpn., 1978, vol. 51, p. 1911.CrossRefGoogle Scholar
  9. 9.
    Uemura, S., Okazaki, H., and Okano, M., J. Chem. Soc., Perkin Trans. 1, 1978, p. 1278.CrossRefGoogle Scholar
  10. 10.
    Bianchini, R., Chiappe, C., Lo Moro, G., Lenoir, D., Lemmen, P., and Goldberg, N., Chem. Eur. J., 1999, vol. 5, p. 1570.CrossRefGoogle Scholar
  11. 11.
    Herges, R., Papafilippopoulos, A., Hess, K., Chiappe, C., Lenoir, D., and Detert, H., Angew. Chem., 2005, vol. 117, p. 1437; Angew. Chem., Int. Ed., 2005, vol. 44, p. 1412.CrossRefGoogle Scholar
  12. 12.
    Yamabe, S., Minato, T., and Inagaki, S., J. Chem. Soc., Chem. Commun., 1988, p. 532.Google Scholar
  13. 13.
    Kurosaki, Y., J. Mol. Struct. (Theochem), 2000, vol. 503, p. 231.CrossRefGoogle Scholar
  14. 14.
    Kurosaki, Y., J. Mol. Struct. (Theochem), 2001, vol. 545, p. 225.CrossRefGoogle Scholar
  15. 15.
    V’yunov, K.A. and Ginak, A.I., Usp. Khim., 1981, vol. 50, p. 273.Google Scholar
  16. 16.
    Zabalov, M.V., Karlov, S.S., Lemenovskii, D.A., and Zaitseva, G.S., J. Org. Chem., 2005, vol. 70, p. 9175.CrossRefGoogle Scholar
  17. 17.
    Chiappe, C., De Rubertis, A., Detert, H., Lenoir, D., Wannere, C.S., and von Schleyer, P.R., Chem. Eur. J., 2002, vol. 8, p. 967.CrossRefGoogle Scholar
  18. 18.
    Selina, A.A., Karlov, S.S., and Zaitseva, G.S., Vestn. Mosk. Gos. Univ., Ser. 2: Khim., 2004, vol. 45, p. 147.Google Scholar
  19. 19.
    Assfeld, X., Garapon, J., Rinaldi, D., Ruiz-Lopez, M.F., and Rivali, J.L., J. Mol. Struct. (Theochem), 2001, vol. 545, p. 225.CrossRefGoogle Scholar
  20. 20.
    Cossi, M., Persico, M., and Tomasi, J., J. Am. Chem. Soc., 1994, vol. 116, p. 5373.CrossRefGoogle Scholar
  21. 21.
    Kurosaki, Y., J. Phys. Chem. A, 2001, vol. 105, p. 11080.CrossRefGoogle Scholar
  22. 22.
    Karlov, S.S., Shutov, P.L., Churakov, A.V., Lorberth, J., and Zaitseva, G.S., J. Organomet. Chem., 2001, vol. 627, p. 1.CrossRefGoogle Scholar
  23. 23.
    Selina, A.A., Karlov, S.S., Harms, K., Tyurin, D.A., Oprunenko, Yu.F., Lorberth, J., and Zaitseva, G.S., Z. Naturforsch., Teil B, 2003, vol. 58, p. 613.Google Scholar
  24. 24.
    Selina, A.A., Karlov, S.S., Gauchenova, E.V., Churakov, A.V., Kuz’mina, L.G., Howard, J.A.K., Lorberth, J., and Zaitseva, G.S., Heteroatom Chem., 2004, vol. 15, p. 43.CrossRefGoogle Scholar
  25. 25.
    Perdew, J.P., Burke, K., and Ernzerhoff, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865.CrossRefGoogle Scholar
  26. 26.
    Ernzerhoff, M. and Scuseria, G.E., J. Chem. Phys., 1999, vol. 110, p. 5029.CrossRefGoogle Scholar
  27. 27.
    Laikov, D.N., Chem. Phys. Lett., 1997, vol. 281, p. 151.CrossRefGoogle Scholar
  28. 28.
    Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Loseki, S., Matsunaga, N., Nguyen, K.A., Su, S.J., Windus, T.L., Dupuis, M., and Montgomery, J.A., J. Comput. Chem., 1993, vol. 14, p. 1347.CrossRefGoogle Scholar
  29. 29.
    Bloemink, H.I., Cooke, S.A., Hinds, K., Legon, A.C., and Thorn, J.C., J. Chem. Soc., Faraday Trans., 1995, vol. 91, p. 1891.CrossRefGoogle Scholar
  30. 30.
    Gergo, E., Hargittai, I., and Schultz, G., J. Organomet. Chem., 1967, vol. 112, p. 29.CrossRefGoogle Scholar
  31. 31.
    Jensen, F.R. and Davis, D.D., J. Am. Chem. Soc., 1971, vol. 93, p. 4048.CrossRefGoogle Scholar
  32. 32.
    Rahm, A. and Pereyre, M., J. Am. Chem. Soc., 1977, vol. 99, p. 1672.CrossRefGoogle Scholar
  33. 33.
    Fukuzumi, S. and Kochi, J.K., J. Am. Chem. Soc., 1980, vol. 102, p. 2141.CrossRefGoogle Scholar
  34. 34.
    Fukuto, J.M. and Jensen, F.R., Acc. Chem. Res., 1983, vol. 16, p. 177.CrossRefGoogle Scholar
  35. 35.
    Lambert, J.B., Wang, G.T., Finzel, R.B., and Teramura, D.H., J. Am. Chem. Soc., 1987, vol. 109, p. 7838.CrossRefGoogle Scholar
  36. 36.
    Brooks, B.R. and Schaefer, H.F., III, J. Am. Chem. Soc., 1979, vol. 101, p. 307.CrossRefGoogle Scholar
  37. 37.
    Han, W.G., Lovell, T., Liu, T., and Noodleman, L., ChemPhysChem, 2002, vol. 3, p. 167.CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2007

Authors and Affiliations

  • M. V. Zabalov
    • 1
  • S. S. Karlov
    • 1
  • D. A. Lemenovskii
    • 1
  • G. S. Zaitseva
    • 1
  1. 1.Faculty of ChemistryMoscow State UniversityMoscowRussia

Personalised recommendations