Ferrocenes with Perfluorinated Side Chains and Ferrocenophanes with Fluorinated Handles

This is the authors' abstract. We don't add key points for this paper.

Trifluorovinyl groups are introduced onto the cyclopentadienyl ligands of ferrocene at the 1-, 1,1'-, and 1,2-positions by Negishi-type and Stille-type coupling reactions of trifluorovinylzinc chloride and tri-n-butyltrifluorovinyl stannane with several iodoferrocenes. Modification of the trifluorovinyl group by nucleophilic substitution and [2+2] cycloaddition make them versatile building blocks for synthetic transformations. 1,1'-Bis(trifluorovinyl) ferrocene reacts upon contact with silica or oxidizing agents and in the presence of a suitable nucleophile through a redox autocatalytic mechanism to afford ferrocenophanes with fluorinated handles. C(F)(H) and C(F)(OMe) moieties in α-positions allowed further modifications to be performed by nucleophilic substitution of the fluorine atoms. A series of ferrocenes with fluorinated side chains and ferrocenophanes with fluorinated handles were isolated and characterized. Several molecular structures were determined by single-crystal X-ray diffraction. The influence of the fluorine substituents on the redox properties of the iron center were studied by cyclic voltammetry.