Skip to main content
SpringerLink
Log in

Key intermediates in metallocene-and post-metallocene-catalyzed polymerization

  • Mechanisms of Catalytic Reactions
  • Published:
Kinetics and Catalysis Aims and scope Submit manuscript

Abstract

The structures of intermediates formed upon the activation by methylaluminoxane (MAO) of a wide range of metallocene and post-metallocene catalysts of olefin polymerization were studied by 13C, 1H, and 19F NMR. For all metallocenes considered (L2ZrCl2 and L2TiCl2), under conditions similar to real polymerization conditions (Al/Zr > 200), two types of intermediates were identified in the reaction solution, namely, heterodinuclear ion pairs [L2 M(μ-Me)2AlMe2]+[Me-MAO]− (III) and zwitterionic intermediates L2 MMe+←Me-Al−≡MAO (IV (M = Zr, Ti). The relative concentration of III increases with an increase in the Al/Zr ratio. In the post-metallocene/MAO catalytic systems, the reaction solution can be dominated either by heterodinuclear pairs of type III (bis(imino)pyridyl iron complexes) or by zwitterionic intermediates of type IV (half-titanocenes, complexes with restricted geometry). Both species III and species IV catalyze olefin polymerization. Both the species initiating polymerization, [L ′2 TiMe(S)]+[Me-MAO]−, and the species responsible for chain growth, [L [L ′2 TiP]+[Me-MAO]− (P is the polymer chain, and S is a solvent molecule), were characterized in the bis(phenoxyimine) titanium complex/MAO system.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Bochmann, M., J. Organomet. Chem., 2004, vol. 689, no. 24, p. 3982.

    Article  CAS  Google Scholar 

  2. Gibson, V.C. and Spitzmesser, S.K., Chem. Rev., 2003, vol. 103, no. 1, p. 283.

    Article  CAS  Google Scholar 

  3. Kaminsky, W., J. Chem. Soc., Dalton Trans., 1998, no. 9, p. 1413.

  4. Chen, E. and Marks, T.J., Chem. Rev., 2000, vol. 100, no. 4, p. 1391.

    Article  CAS  Google Scholar 

  5. Brintzinger, H.-H., Fischer, D., Mulhaupt, R., Rieger, B., and Waymouth, R.M., Angew. Chem., Int. Ed. Engl., 1995, vol. 34, no. 9, p. 1143.

    Article  CAS  Google Scholar 

  6. Matsui, S. and Fujita, T., Catal. Today, 2001, vol. 66, no. 1, p. 63.

    Article  CAS  Google Scholar 

  7. Tritto, I., Donetti, R., Sacchi, M.C., Locatelli, P., and Zannoni, G., Macromolecules, 1997, vol. 30, no. 5, p. 1247.

    Article  CAS  Google Scholar 

  8. Babushkin, D.E., Semikolenova, N.V., Zakharov, V.A., and Talsi, E.P., Macromol. Chem. Phys., 2000, vol. 201, no. 5, p. 558.

    Article  CAS  Google Scholar 

  9. Bryliakov, K.P., Semikolenova, N.V., Yudaev, D.V., Zakharov, V.A., Brintzinger, H.-H., Ystenes, M., Rytter, E., and Talsi, E.P., J. Organomet. Chem., 2003, vol. 683, no. 1, p. 92.

    Article  CAS  Google Scholar 

  10. Bryliakov, K.P., Semikolenova, N.V., Zakharov, V.A., and Talsi, E.P., J. Organomet. Chem., 2003, vol. 683, no. 1, p. 23.

    Article  CAS  Google Scholar 

  11. Bryliakov, K.P., Talsi, E.P., and Bochmann, M., Organometallics, 2004, vol. 23, no. 1, p. 149.

    Article  CAS  Google Scholar 

  12. Bryliakov, K.P., Babushkin, D.E., Talsi, E.P., Voskoboynikov, A.Z., Gritzo, H., Schroder, L., Damrau, H-R.H., Wieser, U., Schaper, F., and Brintzinger, H-H., Organometallics, 2005, vol. 24, no. 5, p. 894.

    Article  CAS  Google Scholar 

  13. Bryliakov, K.P., Semikolenova, N.V., Panchenko, V.N., Zakharov, V.A., Brintzinger, H.-H., and Talsi, E.P., Macromol. Chem. Phys., 2006, vol. 207, no. 3, p. 327.

    Article  CAS  Google Scholar 

  14. Bryliakov, K.P., Kravtsov, E.A., Pennington, D.A., Lancaster, S.J., Bochmann, M., Brintzinger, H.-H., and Talsi, E.P., Organometallics, 2005, vol. 24, no. 23, p. 5660.

    Article  CAS  Google Scholar 

  15. Yang, X., Stern, C.L., and Marks, T.J., J. Am. Chem. Soc., 1991, vol. 113, no. 9, p. 3623.

    Article  CAS  Google Scholar 

  16. Yang, X., Stern, C.L., and Marks, T.J., J. Am. Chem. Soc., 1994, vol. 116, no. 22, p. 10 015.

    Article  CAS  Google Scholar 

  17. Jia, L., Yang, X., Stern, C.L., and Marks, T.J., Organometallics, 1997, vol. 16, no. 5, p. 842.

    Article  CAS  Google Scholar 

  18. Chen, Y.-X., Metz, M.V., Li, L., Stern, C.L., and Marks, T.J., J. Am. Chem. Soc., 1998, vol. 120, no. 25, p. 6287.

    Article  CAS  Google Scholar 

  19. Bochmann, M. and Lancaster, S.J., Angew. Chem., Int. Ed. Engl., 1994, vol. 33, no. 12, p. 1634.

    Article  Google Scholar 

  20. Zhou, J., Lancaster, S.J., Walker, D.A., Beck, S., Thornton-Pett, M., and Bochmann, M., J. Am. Chem. Soc., 2001, vol. 123, no. 2, p. 223.

    Article  CAS  Google Scholar 

  21. Bochmann, M. and Sarsfield, M.J., Organometallics, 1998, vol. 17, no. 26, p. 5908.

    Article  CAS  Google Scholar 

  22. Holton, J., Lappert, M.F., Ballard, D.G.H., Pearce, R., Atwood, J.L., and Hunter, W.E., J. Chem. Soc., Dalton Trans., 1979, no. 1, p. 45.

  23. Ewart, S.W., Sarsfield, M.J., Williams, E.F., and Baird, M.C., J. Organomet. Chem., 1999, vol. 579, nos. 1–2, p. 106.

    Article  CAS  Google Scholar 

  24. Chen, Y., Stern, C.L., and Marks, T.J., J. Am. Chem. Soc., 1997, vol. 119, no. 10, p. 2582.

    Article  CAS  Google Scholar 

  25. Small, B.L., Brookhart, M., and Bennett, A.M.A., J. Am. Chem. Soc., 1998, vol. 120, no. 16, p. 4049.

    Article  CAS  Google Scholar 

  26. Britovsek, G.J.P., Gibson, V.C., Kimberley, B.S., Maddox, P.J., McTavish, S.J., Solan, G.A., White, A.J.P., and Williams, D.J., Chem. Commun., 1998, no. 7, p. 849.

  27. Britovsek, G.J.P., Bruce, M., Gibson, V.C., Kimberley, B.S., Maddox, P.J., Mastroianni, S., McTavish, S.J., Redshaw, C., Solan, G.A., Stromberg, S., White, A.J.P., and Williams, D.J., J. Am. Chem. Soc., 1999, vol. 121, no. 38, p. 8728.

    Article  CAS  Google Scholar 

  28. Britovsek, G.J.P., Gibson, V.C., and Wass, D.F., Angew. Chem., Int. Ed. Engl., 1999, vol. 38, no. 4, p. 428.

    Article  CAS  Google Scholar 

  29. Ittel, S.D., Johnson, L.K., and Brookhart, M., Chem. Rev., 2000, vol. 100, no. 4, p. 1169.

    Article  CAS  Google Scholar 

  30. Mecking, S., Angew. Chem., Int. Ed. Engl., 2001, vol. 40, no. 3, p. 534.

    Article  CAS  Google Scholar 

  31. Babik, S.T. and Fink, G., J. Mol. Catal., 2002, vol. 188, nos. 1–2, p. 245.

    Article  CAS  Google Scholar 

  32. Griffiths, E.A.H., Britovsek, G.J.P., Gibson, V.C., and Gould, I.R., Chem. Commun., 1999, no. 14.

  33. Deng, L.Q., Margl, P., and Ziegler, T., J. Am. Chem. Soc., 1999, vol. 121, no. 27, p. 6479.

    Article  CAS  Google Scholar 

  34. Khoroshun, D.V., Musaev, D.G., Vreven, T., and Morokuma, K., Organometallics, 2001, vol. 20, no. 10, p. 2007.

    Article  CAS  Google Scholar 

  35. Talsi, E.P., Babushkin, D.E., Semikolenova, N.V., Zudin, V.N., Panchenko, V.N., and Zakharov, V.A., Macromol. Chem. Phys., 2001, vol. 202, no. 10, p. 2046.

    Article  CAS  Google Scholar 

  36. Britovsek, G.J.P., Clentsmith, G.K.B., Gibson, V.C., Goodgame, D.M.L., McTavish, S.J., and Pankhurst, Q.A., Catal. Commun., 2002, vol. 3, no. 2, p. 207.

    Article  CAS  Google Scholar 

  37. Bryliakov, K.P., Semikolenova, N.V., Zakharov, V.A., and Talsi, E.P., Organometallics, 2004, vol. 23, no. 22, p. 5375.

    Article  CAS  Google Scholar 

  38. Castro, P.M., Lahtinen, P., Axenov, K., Viidanoja, J., Kotiaho, T., Leskela, M., and Repo, T., Organometallics, 2005, vol. 24, no. 15, p. 3664.

    Article  CAS  Google Scholar 

  39. Scott, J., Gambarotta, S., Korobkov, I., and Budzelaar, P.H.M., J. Am. Chem. Soc., 2005, vol. 127, no. 37, p. 13019.

    Article  CAS  Google Scholar 

  40. Scott, J., Gambarotta, S., Korobkov, I., and Budzelaar, P.H.M., Organometalics, 2005, vol. 24, no. 26, p. 6298.

    Article  CAS  Google Scholar 

  41. Wang, S.B., Liu, D.B., Huang, R.B., Zhang, Y.D., and Mao, B.Q., J. Mol. Catal. A: Chem., 2006, vol. 245, nos. 1–2, p. 122.

    Article  CAS  Google Scholar 

  42. Zakharov, V.A., Semikolenova, N.V., Mikenas, T.B., Barabanov, A.A., Bukatov, G.D., Echevskaya, L.G., and Mats’ko, M.A., Kinet. Katal., 2006, vol. 47, no. 2, p. 303 [Kinet. Catal. (Engl. Transl.), vol. 47, no. 2, p. 303].

    Article  CAS  Google Scholar 

  43. Bart, S.C., Hawrelak, E.J., Lobkovky, E., and Chirik, P.J., Organometallics, 2005, vol. 24, no. 23, p. 5518.

    Article  CAS  Google Scholar 

  44. Ivanchev, S.S., Oleinik, I.I., Ivancheva, N.I., and Oleinik, I.V., Dokl. Phys. Chem., 2005, vol. 404, no. 2, p. 182.

    Google Scholar 

  45. Matsui, S., Mitani, M., Saito, J., Tohi, Y., Makio, H., Tanaka, H., and Fujita, T., Chem. Lett., 1999, p. 1263.

  46. Matsui, S., Mitani, M., Saito, J., Tohi, Y., Makio, H., Matsukawa, N., Takagi, Y., Tsuru, K., Nitabaru, M., Nakano, T., Tanaka, H., Kashiwa, N., and Fujita, T., J. Am. Chem. Soc., 2001, vol. 123, no. 28, p. 6847.

    Article  CAS  Google Scholar 

  47. Matsui, S. and Fujita, T., Catal. Today, 2001, vol. 66, no. 1, p. 63.

    Article  CAS  Google Scholar 

  48. Saito, J., Mitani, M., Mohri, J., Yoshida, Y., Matsui, S., Ishii, S., Kojoh, S., Kashiwa, N., and Fujita, T., Angew. Chem., Int. Ed. Engl., 2001, vol. 40, no. 15, p. 2918.

    Article  CAS  Google Scholar 

  49. Mitani, M., Mohri, J., Yoshida, Y., Saito, J., Ishii, S., Tsuru, K., Matsui, S., Furuyama, R., Nakano, T., Tanaka, H., Kojoh, S., Matsugi, T., Kashiwa, N., and Fujita, T., J. Am. Chem. Soc., 2002, vol. 124, no. 13, p. 3327.

    Article  CAS  Google Scholar 

  50. Mitani, M., Nakano, T., and Fujita, T., Chem. Eur. J., 2003, vol. 9, no. 11, p. 2396.

    Article  CAS  Google Scholar 

  51. Tshuva, E.Y., Goldberg, I., and Kol, M., J. Am. Chem. Soc., 2000, vol. 122, no. 43, p. 10 706.

    Article  CAS  Google Scholar 

  52. Tian, J. and Coates, G.W., Angew. Chem., Int. Ed. Engl., 2000, vol. 39, no. 20, p. 3626.

    Article  CAS  Google Scholar 

  53. Tian, J., Hustad, P.D., and Coates, G.W., J. Am. Chem. Soc., 2001, vol. 123, no. 21, p. 5134.

    Article  CAS  Google Scholar 

  54. Pennington, D.A., Clegg, W., Coles, S.J., Harrington, R.W., Hursthouse, M.B., Hughes, D.L., Light, M.E., Schormann, M., Bochmann, M., and Lancaster, S.J., J. Chem. Soc., Dalton Trans., 2005, no. 3, p. 561.

  55. Corradini, P., Guerra, G., and Cavallo, L., Acc. Chem. Res., 2004, vol. 37, no. 4, p. 231.

    Article  CAS  Google Scholar 

  56. Makio, H. and Fujita, T., Macromol. Symp., 2004, vol. 213, no. 1, p. 221.

    Article  CAS  Google Scholar 

  57. Saito, J., Tohi, Y., Matsukawa, N., Mitani, M., and Fujita, T., Macromolecules, 2005, vol. 38, no. 12, p. 4955.

    Article  CAS  Google Scholar 

  58. Furuyama, R., Mitani, M., Mohri, J., Mori, R., Tanaka, H., and Fujita, T., Macromolecules, 2005, vol. 38, no. 5, p. 1546.

    Article  CAS  Google Scholar 

  59. Saito, J., Suzuki, Y., Makio, H., Tanaka, H., Onda, M., and Fujita, T., Macromolecules, 2006, vol. 39, p. 4023.

    Article  CAS  Google Scholar 

  60. Ivanchev, S.S., Trunov, V.A., Rybakov, V.B., Al’bov, D.V., and Rogozin, D.G., Dokl. Phys. Chem., 2005, vol. 404, no. 1, p. 165.

    Article  CAS  Google Scholar 

  61. Kleinschmidt, R., van der Leek, Y., Reffke, M., and Fink, G., J. Mol. Catal. A: Chem., 1999, vol. 148, nos. 1–2, p. 29.

    Article  CAS  Google Scholar 

  62. Bhriain, N.Ni., Brintzinger, H.-H., Ruchatz, D., and Fink, G., Macromolecules, 2005, vol. 38, no. 6, p. 2056.

    Article  CAS  Google Scholar 

  63. Shiono, T., Yoshida, S., Hagihara, H., and Ikeda, T., Appl. Catal., A, 2000, vol. 200, no. 1, p. 145.

    Article  CAS  Google Scholar 

  64. Ioku, A., Hasan, T., Shiono, T., and Ikeda, T., Macromol. Chem. Phys., 2002, vol. 203, no. 4, p. 748.

    Article  CAS  Google Scholar 

  65. Babushkin, D.E. and Brintzinger, H.-H., Chem. Eur. J., 2007, vol. 13 (in press).

Download references

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090, Russia

    E. P. Talsi, K. P. Bryliakov, N. V. Semikolenova & V. A. Zakharov

  2. University of East Anglia, Norwich, NR4 7TJ, UK

    M. Bochmann

Authors
  1. E. P. Talsi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. K. P. Bryliakov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. N. V. Semikolenova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. V. A. Zakharov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M. Bochmann
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Original Russian Text © E.P. Talsi, K.P. Bryliakov, N.V. Semikolenova, V.A. Zakharov, M. Bochmann, 2007, published in Kinetika i Kataliz, 2007, Vol. 48, No. 4, pp. 521–536.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Talsi, E.P., Bryliakov, K.P., Semikolenova, N.V. et al. Key intermediates in metallocene-and post-metallocene-catalyzed polymerization. Kinet Catal 48, 490–504 (2007). https://doi.org/10.1134/S0023158407040052

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0023158407040052

Keywords

Search

Navigation