Dependence of mechanisms to thermodynamics in the electrochemical study of different electrophiles in the presence of some sulfur nucleophiles

• Published in: Monatshefte für Chemie Vol. 151; no. 9; pp. 1349 - 1364
• Main Authors: Beiginejad, Hadi, Rafiee, Zeinab
• Format: Journal Article
• Language: English
• Published: Vienna Springer Vienna 01.09.2020; Springer Nature B.V
• Subjects: Analytical Chemistry; Chemical reactions; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coulometers; Coulometry; Electrochemical oxidation; Inorganic Chemistry; Mercaptobenzothiazole; Nucleophiles; Organic Chemistry; Original Paper; Oxidation; Physical Chemistry; Reaction mechanisms; Sulfur; Theoretical and Computational Chemistry; Voltammetry; Controlled-potential coulometry; Cyclic voltammetry; Density functional theory; Total change of Gibbs free energy
• ISSN: 0026-9247; 1434-4475
• DOI: 10.1007/s00706-020-02666-7

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