In this work, the mechanism of the palladium-catalysed acetoxylation of benzene C-H has been studied theoretically in detail. Based on experimental studies, a four-step mechanism for this reaction had been proposed, that is, C−H activation of benzene is the rate-determining step which forms an intermediate (k1 pathway) which is subsequently oxidized to produce a high-valent Pd intermediate (k2 pathway). Using quantum chemical calculations, all pathways were investigated, and the activation energy, activation enthalpy and activation Gibbs free energy for all steps were calculated and compared with each other. It was determined that the RDS proceeds through a square complex instead of a T-shaped complex. The activation energy related to the k2 pathway is higher than that of the RDS, and therefore, a new mechanism is proposed.

中文翻译：

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钯催化苯的C-H乙酰氧基化机理的量子化学研究

在这项工作中，从理论上详细研究了钯催化苯 CH 乙酰氧基化的机理。基于实验研究，提出了该反应的四步机制，即苯的 C-H 活化是形成中间体（k1 途径）的限速步骤，随后被氧化产生高价Pd 中间体（k2 途径）。使用量子化学计算，研究了所有途径，并计算了所有步骤的活化能、活化焓和活化吉布斯自由能并相互比较。已确定 RDS 通过方形复合体而不是 T 形复合体进行。与k2途径相关的活化能高于RDS的活化能，因此提出了一种新的机制。