Skip to main content
SpringerLink
Log in

A study of the polymerization of ethylene on Ti(III) monocyclopentadienyl compounds by the density functional theory method

  • Structure of Matter and Quantum Chemistry
  • Published:
Russian Journal of Physical Chemistry A, Focus on Chemistry Aims and scope Submit manuscript

Abstract

Density functional theory was used to study model ethylene reactions with CpTiIIIEt+A− (A− = CH3B(C6F5) −3 , or B(C6F5) −4 ; A− can be absent) compounds. The polymerization of ethylene on an isolated CpTiEt+ cation is hindered because of equilibrium between the CpTi(C2H4)Et+ primary complex and the primary product of CpTiBu+ insertion. At the same time, the polymerization of ethylene on CpTiEt+A− ion pairs (A− = CH3B(C6F5) −3 or B(C6F5) −4 ) is thermodynamically allowed (ΔE from −26.2 to −25.6 kcal/mol and ΔG 298 from −10.9 to −10.4 kcal/mol) and is not related to overcoming substantial energy barriers (ΔE # = 8.2−12.3 kcal/mol and ΔG ≠298 ) = 7.8−13.3 kcal/mol). The degree of polymerization can be low because of the effective occurrence of polymer chain termination by hydrogen transfer from the polymer chain to the monomer.

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. J. C. W. Chien and Z. Salajka, J. Polym. Sci., Part A: Polym. Chem. 29, 1243 (1991).

    Article  CAS  Google Scholar 

  2. J. C. W. Chien and Z. Salajka, J. Polym. Sci., Part A: Polym. Chem. 29, 1253 (1991).

    Article  CAS  Google Scholar 

  3. P. Foster, J. C. W. Chien, and M. D. Rausch, Organometallics 15, 2404 (1996).

    Article  CAS  Google Scholar 

  4. W. Kaminsky and S. Lenk, Macromol. Symp. 118, 45 (1997).

    CAS  Google Scholar 

  5. W. Kaminsky, S. Lenk, V. Scholz, et al., Macromolecules 30, 7647 (1997).

    Article  CAS  Google Scholar 

  6. N. Schneider, M.-H. Prosenc, and H.-H. Brintzinger, J. Organomet. Chem. 545, 291 (1997).

    Article  Google Scholar 

  7. G. X. Xu and E. Ruckenstein, J. Polym. Sci., Part A: Polym. Chem. 37, 2481 (1999).

    Article  CAS  Google Scholar 

  8. R. Quyoum, Q. Wang, M.-J. Tudoret, et al., J. Am. Chem. Soc. 116, 6435 (1994).

    Article  CAS  Google Scholar 

  9. P. Longo, A. Grassi, and L. Oliva, Makromol. Chem. 191, 2387 (1990).

    Article  CAS  Google Scholar 

  10. P. Aaltonen and J. Seppala, Eur. Polym. J. 30(6), 683 (1994).

    Article  CAS  Google Scholar 

  11. P. Aaltonen and J. Seppala, Eur. Polym. J. 31(1), 79 (1995).

    Article  CAS  Google Scholar 

  12. P. Aaltonen, J. Seppala, L. Matilainen, and M. Leskela, Macromolecules 27, 3136 (1994).

    Article  CAS  Google Scholar 

  13. C. Pellecchia, D. Pappalargo, M. D’Arco, and A. Zambelli, Macromolecules 29, 1158 (1996).

    Article  CAS  Google Scholar 

  14. G. Xu and S. Lin, Macromolecules 30, 685 (1997).

    Article  CAS  Google Scholar 

  15. Q. Wu, Z. Ye, Q. Gao, and S. Lin, Macromol. Chem. Phys. 199, 1715 (1998).

    Article  CAS  Google Scholar 

  16. I. E. Nifant’ev, L. Yu. Ustynyuk, and D. V. Besedin, Organometallics 22, 2619 (2003).

    Article  CAS  Google Scholar 

  17. D. N. Laikov, Chem. Phys. Lett. 281, 151 (1997).

    Article  CAS  Google Scholar 

  18. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).

    Article  CAS  Google Scholar 

  19. J. C. W. Lohrenz, T. K. Woo, and T. Ziegler, J. Am. Chem. Soc. 117, 12793 (1995).

    Google Scholar 

  20. T. K. Woo, L. Fan, and T. Ziegler, Organometallics 13, 2252 (1994).

    Article  CAS  Google Scholar 

  21. L. Yu. Ustynyuk, D. V. Besedin, V. V. Lunin, and Yu. A. Ustynyuk, Zh. Fiz. Khim. 77(5), 823 (2003) [Russ. J. Phys. Chem. 77 (5), 733 (2003)].

    CAS  Google Scholar 

  22. I. E. Nifant’ev, L. Yu. Ustynyuk, and D. N. Laikov, Izv. Akad. Nauk, Ser. Khim. 49(7), 1168 (2000).

    Google Scholar 

  23. I. E. Nifant’ev, L. Yu. Ustynyuk, and D. N. Laikov, Izv. Akad. Nauk, Ser. Khim. 49(10), 1754 (2000).

    Google Scholar 

  24. I. E. Nifant’ev, L. Yu. Ustynyuk, and D. N. Laikov, Organometallics 20, 5375 (2001).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Chemistry, Moscow State University, Leninskie gory, Moscow, 119992, Russia

    D. V. Besedin, L. Yu. Ustynyuk & I. E. Nifant’ev

Authors
  1. D. V. Besedin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. Yu. Ustynyuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. I. E. Nifant’ev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to L. Yu. Ustynyuk.

Additional information

Original Russian Text © D.V. Besedin, L.Yu. Ustynyuk, I.E. Nifant’ev, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 11, pp. 2096–2107.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Besedin, D.V., Ustynyuk, L.Y. & Nifant’ev, I.E. A study of the polymerization of ethylene on Ti(III) monocyclopentadienyl compounds by the density functional theory method. Russ. J. Phys. Chem. 82, 1885–1895 (2008). https://doi.org/10.1134/S0036024408110162

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0036024408110162

Keywords

Search

Navigation