Electrochemical and spectroscopic studies of 2,3-dihydroxybenzoic acid,its oxidation products and their interaction with manganese(II), in dimethyl sulfoxide solutions

The electrochemical and spectroscopic behaviour of 2,3-dihydroxybenzoic acid (2,3-DHBA) and its oxidized forms have been studied in dimethyl sulfoxide solutions under aerobic and anaerobic conditions. The products resulting from the reaction with manganese(II) (in dimethyl sulfoxide) are also studied by cyclic voltammetry, u.v–vis., n.m.r. and e.s.r. spectroscopies. Under anaerobic conditions the anions of the ligand form stable complexes with manganese(II) and (III) of MnL₂ type, while in the presence of air the oxidized forms of the ligand react with manganese(II) to give mixed-valence species. The chemical stability of the semiquinone and its manganese complexes in addition to its photosensitivity is noteworthy. Calculations show that the electrogenerated manganese(III)–(2,3-DHB–semiquinone) system is stable, but redox-active and can undergo a two-electron exchange (per monomer). The dimeric (or oligomeric) species should be good candidates for water oxidation studies.