Electrochemical study of different electrophiles in the presence of p-toluenesulfinic acid and 2-mercaptobenzothiazole as sulfur nucleophiles was investigated. Mechanistic study of the electrochemical reactions indicates that the electrochemical oxidation of some species in the presence of the sulfur groups has different mechanisms, but some other species in the presence of both sulfur nucleophiles have the same mechanism. To explain the reason for this difference, the computational study was used. Thermodynamic investigation shows that when ∆G_tot of the electrochemical oxidation of products are less than that of initial species, the electrochemically produced species can be oxidized during controlled-potential coulometry. The results of this work indicate that the computational study can be used to justify the reaction mechanisms. Cyclic voltammetry, linear sweep voltammetry, and controlled-potential coulometry were used to obtain the experimental results. Also, by the use of BP86 level of theory and 6–31 + G(d,p) basis set, the theoretical data were obtained.

Graphic abstract

中文翻译：

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在某些硫亲核试剂存在下不同亲电试剂的电化学研究中，热力学机理的依赖性

研究了在对甲苯磺酸和2-巯基苯并噻唑作为硫亲核试剂存在下不同亲电试剂的电化学研究。电化学反应的机理研究表明，某些物种在存在硫基的情况下的电化学氧化机理不同，但在另两种硫亲核试剂存在下的其他物种则具有相同的机理。为了解释这种差异的原因，使用了计算研究。热力学研究表明，当ΔG _tot产物的电化学氧化比初始物种少，电化学产生的物种可以在控制电位库仑法中被氧化。这项工作的结果表明，计算研究可用于证明反应机理的合理性。使用循环伏安法，线性扫描伏安法和控制电位库仑法获得实验结果。此外，通过使用BP86理论水平和6–31 + G（d，p）基集，可以获得理论数据。

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