Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Mechanism of the catalytic action of the mechanoactivated salt K2PTCL4 in the gas-phase hydrochlorination of acetylene

  • 38 Accesses

  • 1 Citations


A heterogeneous catalyst for the hydrochlorination of acetylene by gaseous HCl is formed as a result of mechanical treatment of the solid salt K2PtCl4 in an atmosphere of acetylene, ethylene, or propylene by the formation of π complexes of platinum(II) as active centers in the surface layer under these conditions. The controlling stage of the catalytic reaction is chloroplatination of the π-coordinated acetylene by the HCl molecule. The reaction takes place as a concerted process, in which an intermediate β-chlorovinyl derivative of platinum(II), a complex of platinum with a coordination vacancy[PtCl 3 * ], and a new molecule of HCl are formed simultaneously with cleavage of the H—Cl and Pt—Cl bonds in the metal complex adjacent to the π-acetylene complex. The catalytic cycle closes with rapid dissociation of the organoplatinum intermediate by the action of HCl, giving the final product and the initial complex [PtCl4]2−.

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


  1. 1.

    P. T. Anastas and J. C. Wamer, Green Chemistry: Theory and Practice, Oxford Sci. Publ., Oxford (1998).

  2. 2.

    V. D. Pokhodenko and V. V. Pavlishchuk, Teor. Éksp. Khim., 38, No. 2, 67–83 (2002).

  3. 3.

    P. Yu. Butyagin, Kinet. Katal., 28, No. 1, 5 (1987).

  4. 4.

    I. R. Subbotina, B. N. Shelimov, and V. B. Kazanskii, Kinet. Katal., 39, No. 1, 87 (1998).

  5. 5.

    S. A. Mitchenko, E. V. Khomutov, A. A. Shubin, and Yu. M. Shul’ga, J. Mol. Catal. A, 212, 345–352 (2004).

  6. 6.

    P. Yu. Butyagin, Usp. Khim., 63, No. 12, 1031 (1994).

  7. 7.

    O. N. Temkin, G. K. Shestakov, and Yu. A. Treger, Acetylene: Chemistry. Reaction Mechanisms. Technology, O. N. Temkin (ed.), Khimiya, Moscow (1991).

  8. 8.

    R. S. Mitchenko, A. A. Shubin, and A. N. Vdovichenko, Teor. Éksp. Khim., 42, No. 3, 173–177 (2006).

  9. 9.

    S. A. Mitchenko, E. V. Khomutov, V. V. Kovalenko, et al., Inorg. Chim. Acta, 320, Nos. 1/2, 31–37 (2001).

  10. 10.

    M. Herberhold, π-Complexes of Metals. Complexes with Monoolefinic Ligands [Russian translation], Mir, Moscow (1975).

  11. 11.

    JCPDS: International Centre for Diffraction Data, N 9-367.

  12. 12.

    L. Melander and W. Saunders, Reaction Rates of Isotopic Molecules [Russian translation], Mir, Moscow (1983).

  13. 13.

    A. Gordon and R. Ford, The Chemist’s Companion, Wiley-Interscience (1973).

  14. 14.

    I. N. Chernyaev (ed.), Synthesis of Complex Compounds of Metals of the Platinum Group, Nauka, Moscow (1964).

  15. 15.

    F. M. Rapoport and A. A. Il’inskaya, Laboratory Methods for the Production of Pure Gases [in Russian], Goskhimizdat, Moscow (1963), p. 362.

Download references

Author information

Additional information


Translated from Teoreticheskaya i Éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 306–311, September–October, 2006.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Mitchenko, R.S., Shubin, A.A. & Krasnyakova, T.V. Mechanism of the catalytic action of the mechanoactivated salt K2PTCL4 in the gas-phase hydrochlorination of acetylene. Theor Exp Chem 42, 314–319 (2006). https://doi.org/10.1007/s11237-006-0059-7

Download citation

Key words

  • acetylene
  • heterogeneous catalysis
  • hydrochlorination
  • reaction mechanism
  • mechanoactivation
  • platinum complexes