Abstract
The electrochemical behavior of the species [Co(η5-C5H5)(η3-2-MeC3H4)I] and [Co(η5-C5H5)(η3-2-MeC3H4)(ACN)]+ in ACN solutions, at 25 °C, is described. The kinetic analysis of the cyclic voltammetry curves indicates that the introduction of one electron in the former complex is concerted with the dissociation of the Co−I bond. The ensuing radical undergoes fast solvation to yield the solvato complex [Co(η5-C5H5)(η3-2-MeC3H4)(ACN)]•, which then acts as an efficient electron donor toward the starting material with the formation of [Co(η5-C5H5)(η3-2-MeC3H4)(ACN)]+; finally, the cation is electroreduced at the working potentials to conclude an overall autocatalytic sequence. The solvato complex [Co(η5-C5H5)(η3-2-MeC3H4)(ACN)]•, formed as a product of the above reduction process, can be reversibly reduced to the corresponding anion at more negative potentials. Confirmation of the above mechanism and of the fact that the solvato complex can act as a solution electron donor toward the starting material was obtain...
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