ELECTROCHEMISTRY OF OXYGENATION CATALYSTS .6. ELECTROSYNTHESIS, STRUCTURE, ANALYTICAL AND ELECTROCHEMICAL PROPERTIES OF MONOMERIC [CO-III(SALEN)(DMF)(2)](-) SALTS (X=PF6, CLO4)() X()

[Co-III(salen)(DMF)(2)](+) X(-) salts [X = PF6, ClO4; salen = bis(sali cyliden)ethylendiiminato; DMF = dimethylformamide] have been synthesiz ed by electrochemical and chemical (air) oxidation of Co (salen). Thei r monomeric structure with two DMF molecules in the axial positions in both the solid state and DMF solution is shown by X-ray crystal struc ture analysis, thermal analysis, mass spectroscopy, and H-1 and C-13 N MR spectroscopy The electrochemical reduction of the [Co-III(salen)(DM F)(2)](+) cation is investigated by cyclic voltammetry and compared to the oxidation of the neutral Co-III(salen). The redox reaction connec ting the cobalt(II) and the cobat(III) species appears to be a quasi-r eversible electron transfer. These properties make the [Co-III(salen)( DMF)(2)](+) X(-) salts starting materials for the analysis of the inte raction of basic substrates with cobalt(III) species in the context of the biomimetic oxygenation reactions catalyzed by such complexes.