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Mechanisms of the Catalytic Hydrochlorination of Acetylene: Active Sites, Isotope Effects, and Stereoselectivity

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Abstract

The mechanisms of acetylene vapour-phase hydrochlorination over chloro complexes of noble metals were reviewed. The nature of the active sites of heterogeneous catalysts, isotope effects of HCl/DCl, stereochemistry of reaction products, possible stepwise mechanisms, and mechanisms of individual steps were considered.

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Notes

  1. In aqueous solutions, the PtII chloride complexes catalyze the hydrochlorination of acetylene, while the PtIV chloride complexes do not show any appreciable catalytic activity [29].

  2. For terminal carbonyls, νСО is generally shifted toward long waves relative to the 2143 cm–1 of free СО and lies between 2125 and 1850 cm–1 [38].

  3. The stretching vibrations of the С≡С triple bond generally show themselves in the range 2260–2190 cm–1 [41]. A small bathochromic shift is the consequence of the binding of acetylene in the π-complex.

  4. The stoichiometric consequence of the acetylene chloropalladation step is the formation of a PdII chlorovinyl derivative and adjacent palladium complex lying on the (100) crystallographic plane with a coordination vacancy that bears a local positive charge.

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Funding

This study was financially supported by the Ministry of Education and Science of the Russian Federation under the government contract for R&D (application no. 10.2980.2017/4.6).

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Authors and Affiliations

  1. Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, 83114, Donetsk, Ukraine

    T. V. Krasnyakova, D. V. Nikitenko & S. A. Mitchenko

  2. Taras Shevchenko National University of Lugansk, 91011, Lugansk, Ukraine

    T. V. Krasnyakova

  3. Platov South-Russian State Polytechnic University, 346400, Novocherkassk, Russia

    S. A. Mitchenko

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  1. T. V. Krasnyakova
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Translated by L. Smolina

Abbreviations: VCM, vinyl chloride monomer; PVC, polyvinyl chloride; DCE, dichloroethane; KIE, kinetic isotope effect; γ, product isotope effect; TEMPO, 2,2,6,6-tetramethylpiperidin-1-yl)oxyl; DRIFT, diffuse reflection infrared Fourier transform spectroscopy; EDS SEM, energy dispersive X-ray spectroscopy with scanning electron microscopy; TOF, specific catalytic activity (turnover frequency); HAADF-STEM, high-angle annular dark-field scanning transmission electron microscopy; XAFS, X-ray absorption fine structure spectroscopy; XPS, X-ray photoelectron spectroscopy; EPR, electron paramagnetic resonance; NMR, nuclear magnetic resonance; HRTEM, high-resolution transmission electron microscopy; SAXS, small-angle X-ray scattering; WAXS, wide-angle X-ray scattering; RDF, radial distribution function; RED, radial electron density distribution; DFT, density functional theory.

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Krasnyakova, T.V., Nikitenko, D.V. & Mitchenko, S.A. Mechanisms of the Catalytic Hydrochlorination of Acetylene: Active Sites, Isotope Effects, and Stereoselectivity. Kinet Catal 61, 58–79 (2020). https://doi.org/10.1134/S0023158420010036

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