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Influence of components of the PdCl2(PPh3)2-PPh3-p-toluenesulfonic acid catalytic system on the rate of cyclohexene hydrocarbalkoxylation with m-cresol

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Abstract

Kinetic parameters were determined for the cyclohexene hydrocarbalkoxylation reaction catalyzed by the PdCl2(PPh3)2-PPh3-p-toluenesulfonic acid (TSA) catalyst system in the presence of m-cresol. It was shown that the reaction is first order in cyclohexene and a fractional order in PdCl2(PPh3)2 and m-cresol and that the dependences of the reaction rate on PCO, TSA and PPh3 concentrations are nonmonotonic in character. The inhibitory effect of tosylate and chloride ions on the reaction was revealed. The results were rationalized in terms of a mechanism that involves hydride complexes of the cation type as intermediates. A rate equation for the reaction was derived in terms of the steady-state hypothesis to fit to experimental data.

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Authors and Affiliations

  1. Tula State University, Tula, Russia

    V. A. Aver’yanov, N. M. Nosova, E. V. Astashina & N. T. Sevost’yanova

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  1. V. A. Aver’yanov
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  2. N. M. Nosova
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  3. E. V. Astashina
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  4. N. T. Sevost’yanova
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Original Russian Text © V.A. Aver’yanov, N.M. Nosova, E.V. Astashina, N.T. Sevost’yanova, 2007, published in Neftekhimiya, 2007, Vol. 47, No. 3, pp. 186–195.

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Aver’yanov, V.A., Nosova, N.M., Astashina, E.V. et al. Influence of components of the PdCl2(PPh3)2-PPh3-p-toluenesulfonic acid catalytic system on the rate of cyclohexene hydrocarbalkoxylation with m-cresol. Pet. Chem. 47, 167–175 (2007). https://doi.org/10.1134/S0965544107030048

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  • DOI: https://doi.org/10.1134/S0965544107030048

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