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Effect of temperature and CO pressure on the rate of cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)2-PPh3-TsOH system

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Abstract

The quantitative regularities of the effect of CO pressure and temperature on the rate of cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)2-PPh3-TsOH system were defined. Extremal dependences of the reaction rate on the CO pressure were revealed in the temperature range from 353 to 383 K. To interpret the obtained results, the catalytic cycle was constructed which included the hydride, alkyl, and acyl palladium complexes of the cationic type as intermediates. It was proposed that the catalyst is partially converted into an inactive form due to the exchange between ligands. The experiments on the effect of the CO pressure on the reaction rate made it possible to estimate the apparent rate constants for the kinetic reaction equation obtained earlier.

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Correspondence to N. T. Sevostyanova.

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According to the materials of the International Symposium “Modern Trends in Organometallic Chemistry and Catalysis“ (June 3–7, 2013, Moscow).

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0837–0842, April, 2014.

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Sevostyanova, N.T., Averyanov, V.A., Batashev, S.A. et al. Effect of temperature and CO pressure on the rate of cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)2-PPh3-TsOH system. Russ Chem Bull 63, 837–842 (2014). https://doi.org/10.1007/s11172-014-0518-6

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  • DOI: https://doi.org/10.1007/s11172-014-0518-6

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