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

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Abstract

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−.

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

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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

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Key words

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