Investigation of the Dependence of the Rate of Cyclohexene Alkoxycarbonylation with Cyclohexanol and CO on the p-Toluenesulfonic Acid Monohydrate Concentration and Temperature

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2024-09-11 DOI:10.1134/S0965544124040042

N. T. Sevostyanova, S. A. Batashev

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Abstract

The effects of the p-toluenesulfonic acid monohydrate (TsOH∙H₂O) concentration on the alkoxycarbonylation of cyclohexene over a Pd(PPh₃)₂Cl₂–PPh₃–TsOH∙H₂O catalytic system were quantified at 363–383 K. Within this temperature range, the correlation between the cyclohexyl cyclohexanecarboxylate production rate and the TsOH∙H₂O concentration was found to be similar to an S-shaped curve. Based on these data, as well as previous findings with regard to the effects of water and TsOH∙H₂O concentrations on the cyclohexene methoxycarbonylation rate, the hydride mechanism for the alkoxycarbonylation process was updated by adding relevant ligand exchange reactions between ballast palladium complexes, specifically reactions that produce a palladium aqua complex. The accordingly-modified kinetic equation for cyclohexene alkoxycarbonylation with cyclohexanol and CO was found to be consistent with the experimental data. Effective constants were evaluated for the modified kinetic equation over the studied temperature range. A number of relevant parameters—namely, the effective activation energy and the changes in enthalpy, entropy, and Gibbs free energy during the ligand exchange between the complexes Pd(PPh₃)₂(C₆H₁₁OH)₂ and Pd(PPh₃)₂(H₂O)₂—were further evaluated in light of the activated complex theory. This reaction was found to be nearly equilibrium at 373 K.

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研究环己醇与 CO 发生环己烯烷氧基羰基化的速率与对甲苯磺酸一水合物浓度和温度的关系

摘要在 363-383 K 的温度范围内，定量研究了对甲苯磺酸一水合物（TsOH∙H2O）浓度对 Pd(PPh3)2Cl2-PPh3-TsOH∙H2O 催化体系上环己烯烷氧基羰基化的影响。根据这些数据以及之前关于水和 TsOH∙H2O 浓度对环己烷甲氧基羰基化速率影响的研究结果，更新了烷氧基羰基化过程的氢化物机理，增加了压载钯络合物之间的相关配体交换反应，特别是产生钯水络合物的反应。相应修改后的环己烯与环己醇和 CO 进行烷氧基羰基化的动力学方程与实验数据一致。在所研究的温度范围内，对修正动力学方程的有效常数进行了评估。根据活化配合物理论，进一步评估了一些相关参数，即 Pd(PPh3)2(C6H11OH)2 和 Pd(PPh3)2(H2O)2 配合物之间配体交换过程中的有效活化能以及焓、熵和吉布斯自由能的变化。结果发现，在 373 K 时，该反应接近平衡。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.