Ferricenium Ion Research Articles

Gamma radiolysis of ferrocene in carbon tetrachloride

Abstract Gamma radiolysis of solutions of ferrocene in carbon tetrachloride results in the disappearance of the solute and in the formation of ferricenium ion and inorganic iron ions. Measured yields are G(-ferrocene) = 2.88, G(ferricenium) = 1.54, and G(inorganic iron) = 1.3. The excellent mass balance with respect to iron indicates the absence of any organo-iron products other than ferricenium ion. The ratio G(ferricenium)/G(inorganic iron) of 1.18 gives support to the recent view that the major product of the radiolysis is the complex ferricenium tetra-chloroferrate although, since the ratio is rather greater than unity, it would appear that some simple ferricenium chloride is also produced. These experimental results contrast with an early study of the ferrocene-carbon tetrachloride system in which it was claimed that at least 95 per cent of the ferrocene destroyed could be accounted for as ferricenium chloride. A possible explanation of these contradictory conclusions is advanced, based on the use of...

Polarized absorption spectra of single crystals of ferrocene and its molecular complexes

The polarized absorption spectra in the 9–40 rK region were observed on small single crystals of ferrocene, ferrocene-TCNE comples and ferricenium picrate by using a microspectrophotometer. It is shown that the 22.7 and 30.5 kK band systems of ferrocene cyrstal can be quantitatively explained on the basis of oriented-gas model. The solid molecular complex of ferrocene and TCNE is confirmed to be of charge-transfer type. The charge-transfer band is strongly polarized in the direction of [1 1 0] axis of crystal. It is concluded that the overlap between the π-electron orbital of cyclopentadienyl ring of ferrocene and that of TCNE is of primary importance in the charge-transfer interaction between ferrocene and TCNE molecules. The sharp absorption band of ferricenium ion located at 16 kK is shown to appear in the crystal spectrum of ferricenium picrate without appreciable change in the location of peak as well as in the band shape. No charge-transfer band can be found in the low-energy region of the spectrum of this crystal.

Substituent effects in the chronopotentiometric oxidation of ferrocene derivatives. Internal solvation of certain substituted ferricenium ions

Substituent effects in the chronopotentiometric oxidation of ferrocene derivatives. Internal solvation of certain substituted ferricenium ions

Free-Radical Phenylation of Ferricenium Ion

Free-Radical Phenylation of Ferricenium Ion