CYCLIC VOLTAMMETRY OF SOME FERROCENEPHANES IN ACETONITRILE

On the basis of cyclic voltammetry measurements in acetonitrile solutions, on the gold working electrode, and using Et4NCIO4 as a supporting electrolyte, the quasi-reversible reaction has been examined: Fcx+ + e reversible Fcx for 20 derivatives of ferrocene containing the substituent chains 1,1'-alkyl, -carboxyl, -hydroxyl, -ether, -thioether etc. groups. The Hammett's substituent parameters sigma-p are calculated from these results using the empirical equation: DELTA-Ef(o) (vs Fc+, Fc) = 0.450-SIGMA-sigma-p + 0.022 V. The influence of 1,1' substituted groups on the electrode reaction parameters of the investigated compounds and the mechanism of the two-step biferrocene redox reaction are discussed.