Add time:08/13/2019         Source:sciencedirect.com

The voltammetric characteristics of the title adducts [Co(Cp) (S2C2X2L] (X CN, CF3, COOCH3, 4-pyridyl, phenyl; L = tributylphosphane or tributyl phosphite) in acetonitrile solutions are reported. Both the phosphane and the phosphite adducts were oxidized and reduced through one-electron transfer processes followed by homogeneous chemical reactions for all X except phenyl; the oxidized adduct dissociated into the free complexes [CoIII (Cp) (S2C2X2] and the cation radical L+·, and the reduced adduct rapidly dissociated into the reduced form of the free complexes [CoII(Cp) (S2C2X2)]− and L. When X = phenyl, the oxidation was similar but the reduction was preceded by the dissociation of L. The oxidation and reduction half-wave potentials of the adducts were more negative than those of the corresponding free complexes, and they were linearly dependent on the adduct formation constant.

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