Russian Journal of Physical Chemistry B

, Volume 13, Issue 2, pp 245–252 | Cite as

Hydrocarbomethoxylation of Cyclohexene Catalyzed by Pd(OAc)2-PPh3-p-Toluenesulfonic Acid. Some Aspects of Reaction Kinetics and Thermodynamics of Ligand Exchange between Palladium Complexes

  • N. T. Sevost’yanovaEmail author
  • S. A. Batashev
  • A. S. Rodionova
Kinetics and Mechanism of Chemical Reactions. Catalysis


The quantitative regularities of the effect of the concentration of promoting additive PPh3 on the rate of hydrocarbomethoxylation of cyclohexene for catalysis with Pd(OAc)2-PPh3-p-Toluenesulfonic acid system are established within the temperature range 368–383 K. It has been shown that in the studied temperature range the dependences of reaction rate on the PPh3 concentration pass through maxima. The results obtained are interpreted within a hydride mechanism of hydrocarbomethoxylation previously proposed. The values of some effective constants of the kinetic reaction equation are estimated. Using the temperature dependence of an effective rate constant, effective activation energy is estimated and, on its basis, the changes in enthalpy, entropy, and Gibbs energy in the ligand exchange reaction between the Pd(PPh3)4 and Pd(CO)2(PPh3)2, 2 complexes were estimated. It is established that this reaction is close to an equilibrium state at 373 K. Using previously obtained data for the temperatures of 363, 368, 373, 378, and 383 K, kinetic models of cyclohexene hydrocarbomethoxylation were developed, reflecting the cumulative effect of various participants in the reaction on its rate and working throughout the reaction.


hydrocarbomethoxylation cyclohexene methyl cyclohexanecarboxylate palladium acetate(II) triphenylphosphine kinetic model ligand exchange 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Kh. A. Suerbaev, N. Zh. Kudaibergenov, and A. Vavasori, Russ. J. Gen. Chem. 87, 707 (2017).CrossRefGoogle Scholar
  2. 2.
    Kh. A. Suerbaev, N. Zh. Kudaibergenov, and A. K. Kurmansitova, Russ. J. Gen. Chem. 86, 2124 (2016).CrossRefGoogle Scholar
  3. 3.
    M. Rosales, I. Pacheco, J. Medira, J. Fernandez, A. Gonzalez, et al., Catal. Lett. 144, 1717 (2014). CrossRefGoogle Scholar
  4. 4.
    M. Amézquita-Valencia, G. Achonduh, and H. Alper, Org. Chem. 80, 6419 (2015). CrossRefGoogle Scholar
  5. 5.
    M. Lemberg and G. Sadowski, J. Chem. Eng. Data 61, 3317 (2016). CrossRefGoogle Scholar
  6. 6.
    P. Pongrácz, A. Abu Seni, L. T. Mika, and L. Kollár, Mol. Catal. 438, 15 (2017). CrossRefGoogle Scholar
  7. 7.
    M. Queirolo, A. Vezzani, R. Mancuso, B. Gabriele, M. Costa, and N.D. Ca', J. Mol. Catal. A 398, 115 (2015). CrossRefGoogle Scholar
  8. 8.
    J. Liu, Q. Liu, R. Franke, R. Jackstell, and M. Beller, J. Am. Chem. Soc. 137, 8556 (2015). CrossRefGoogle Scholar
  9. 9.
    G. Kiss, Chem. Rev. 101, 3435 (2001). CrossRefGoogle Scholar
  10. 10.
    A. Vavasori, L. Toniolo, and G. Cavinato, J. Mol. Catal. A 191, 9 (2003). CrossRefGoogle Scholar
  11. 11.
    V. A. Averyanov, N. T. Sevost'yanova, S. A. Batashev, A. A. Vorob'ev, and A. S. Rodionova, Russ. J. Phys. Chem. B 8, 140 (2014). CrossRefGoogle Scholar
  12. 12.
    I. E. Nifant'ev, N. T. Sevostyanova, V. A. Averyanov, et al., Appl. Catal., A 449, 145 (2012). CrossRefGoogle Scholar
  13. 13.
    A. Vavasori, G. Cavinato, and L. Toniolo, J. Mol. Catal. A 176, 11 (2001). CrossRefGoogle Scholar
  14. 14.
    I. Nifant'ev, N. Sevostyanova, S. Batashev, A. Vorobiev, and A. Tavtorkin, React. Kinet. Mech. Catal 116, 63 (2015). CrossRefGoogle Scholar
  15. 15.
    I. E. Nifant'ev, S. A. Batashev, S. A. Toloraya, et al., J. Mol. Catal. A 350, 64 (2011). CrossRefGoogle Scholar
  16. 16.
    N. T. Sevost'yanova, S. A. Batashev, and A. S. Rodionova, Russ. J. Phys. Chem. B 10, 231 (2016). CrossRefGoogle Scholar
  17. 17.
    A. Seayad, S. Jayasree, K. Damodaran, L. Toniolo, and R. V. Chaudhari, J. Organomet. Chem. 601, 100 (2000). CrossRefGoogle Scholar
  18. 18.
    N. T. Sevost'yanova, V. A. Averyanov, S. A. Batashev, A. S. Rodionova, and A. A. Vorob'ev, Russ. Chem. Bull. 63, 837 (2014).CrossRefGoogle Scholar
  19. 19.
    V. A. Aver'yanov, N. T. Sevost'yanova, and S. A. Batashev, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 55 (4), 111 (2012).Google Scholar
  20. 20.
    H. Yoshida, N. Sugita, K. Kudo, and Y. Takezaki, Bull. Chem. Soc. Jpn. 49, 2245 (1976). CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • N. T. Sevost’yanova
    • 1
    Email author
  • S. A. Batashev
    • 1
  • A. S. Rodionova
    • 1
  1. 1.Tula State Lev Tolstoy Pedagogical UniversityTulaRussia

Personalised recommendations