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R. S. Mitchenko A. A. Shubin T. V. Krasnyakova 《Theoretical and Experimental Chemistry》2006,42(5):314-319
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. 相似文献
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T. V. Krasnyakova D. V. Nikitenko E. V. Khomutova S. A. Mitchenko 《Kinetics and Catalysis》2017,58(5):533-540
Two routes of catalytic hydrochlorination of acetylene were found by the isotopic label method for systems with supported palladium K2PdCl4/C and Н2PdCl4/C catalysts: with formation of the products of syn- and anti-addition of the H(D)Cl molecule to the triple bond of acetylene. Two isotopic effects that differ in magnitude were determined for these systems from the reaction kinetics and the ratio of the yields of the nondeuterated and monodeuterated isotopomers of the product, which are due to the participation of the H(D)Cl molecule in the two reaction stages: limiting chloropalladation and rapid protodemetallation. The effective activation energies and kinetic isotope effects coincided within the experimental errors, which suggests that the reaction mechanisms are similar and the active centers of the catalysts in systems with K2PdCl4/C and Н2PdCl4/C are of the same nature. 相似文献
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S. A. Mitchenko T. V. Krasnyakova I. V. Zhikharev 《Theoretical and Experimental Chemistry》2008,44(5):316-319
We report the catalysis of the hydrochlorination of acetylene on the surface of dry K2PdCl4 subjected to prior mechanical activation in an atmosphere of acetylene or propylene. The stereochemistry of the reaction
corresponds to trans addition of the halogen and hydrogen atoms to the C-C triple bond. The hydrogen halide is the source
of the halogen atom in the reaction product. The mechanical activation of K2PdCl4, in contrast to the case of K2PtCl4, is also capable of activating the C-C double bond: propylene is hydrochlorinated under similar conditions to isopropyl chloride.
Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 306–309, September–October, 2008. 相似文献
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The reaction of iodomethane and acetylene in the presence of PtII and NaI in acetone gives (E)-1-iodopropene. A possible mechanism involves the intermediate formation of a PtIV methyl vinyl derivative by the iodoplatination of acetylene with a reversibly formed a PtIV methyl complex and assumes the catalytic character of the process. 相似文献
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O.?V.?Khazipov M.?A.?Merzlikina D.?V.?Nikytenko E.?V.?Khomutova T.?V.?Krasnyakova S.?A.?MitchenkoEmail author 《Russian Journal of General Chemistry》2017,87(1):128-131
Oxidation state of iodide complexes of PtII and PtIV in large excess of NaI with respect to platinum in water and acetone solution has been determined by means of 195Pt NMR spectroscopy. In acetone, iodide complexes of PtIV are almost quantitatively reduced into PtII, and iodine is bound in a poorly soluble polymeric complex with sodium iodide and acetone. Iodometric titration has revealed the formation of equivalent amount of iodine. Reduction of platinum has not been observed in aqueous medium. 相似文献
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Soromotin V. N. Yakovenko R. E. Krasnyakova T. V. Svetogorov R. D. Mitchenko S. A. 《Kinetics and Catalysis》2022,63(6):765-772
Kinetics and Catalysis - The effect of the gas recirculation mode on the selectivity and deactivation rate of the Co-Al2O3/SiO2 catalyst of the Fischer?Tropsch synthesis at high pressure (6... 相似文献
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S. A. Mitchenko T. V. Krasnyakova I. V. Zhikharev 《Theoretical and Experimental Chemistry》2010,46(1):32-38
A heterogeneous catalyst for the hydrochlorination of acetylene using gaseous HCl was obtained by prior mechanical activation
of K2PdCl4 powder in an atmosphere of acetylene or propylene. Active sites are formed during the mechanical treatment in the surface
layers of the catalyst, which are Pd(II) complexes with a coordination vacancy. 相似文献