Mechanistic Study on the Electrochemical Reduction of 9,10-Anthraquinone in the Presence of Hydrogen-bond and Proton Donating Additives

• Published in: Analytical Sciences Vol. 28; no. 3; p. 257
• Main Authors: KATSUMI, Jiro, NAKAYAMA, Tatsushi, ESAKA, Yukihiro, UNO, Bunji
• Format: Journal Article
• Language: English
• Published: Singapore The Japan Society for Analytical Chemistry 2012; Springer Nature Singapore; Japan Science and Technology Agency
• Subjects: Analytical Chemistry; Anodic; Anthraquinones - chemistry; Antineoplastic Agents - chemistry; Chemistry; Electrochemistry; Electron Transport; Hydrogen Bonding; Mathematical analysis; Original Papers; Pathways; Phenol; Protonation; Protons; Reduction; Simulation
• ISSN: 0910-6340; 1348-2246
• DOI: 10.2116/analsci.28.257

The electrochemical reduction of 9,10-anthraquinone (AQ) was investigated in CH3CN in both the absence and presence of the hydrogen-bond and proton donating additives, CH3OH, CH(CF3)2OH, phenol, 4-methoxyphenol, 4-cyanophenol, 2,4,6-trichlorophenol, and benzoic acid (BA). Three clearly different types of electrochemical behavior were observed with increasing concentrations of the additives, and were simulated to analyze the reaction mechanisms. Type I was observed for weakly interacting additives, such as CH3OH, characterized by positive shifts of the two well-separated reduction waves, corresponding to the formation of AQ•− and AQ2−, with no loss of reversibility. The second wave shifted more strongly, and finally merged with the first. These behaviors are explained by the association of AQ2− with the additives via strong hydrogen-bonding. Type II is attributed to a reduction mechanism involving quantitative formation of strong hydrogen-bonded complexes of AQ2− with additives, such as CH(CF3)2OH, phenol and 4-methoxyphenol, showing a reversible or quasireversible two-electron reduction wave with increasing concentrations of the additives. The behavior of Type III, observed in the presence of strongly interacting additives, such as 2,4,6-trichlorophenol and BA, is characterized by a voltammogram composed of the 2-electorn cathodic and the broad anodic waves without keeping reversibility, facilitated by proton transfer in the hydrogen-bonded complexes, AQ•−-BA and AQ2−-BA. The effects of hydrogen-bonding and protonation on the electrochemistry of AQ have been systematically demonstrated in terms of the potentials and reaction pathways of the various species, which appear in quinone-hydroquinone systems.