title: Ferrocenes with perfluorinated side chains and ferrocenophanes with fluorinated handles.
abstract: 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.
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstrasse 34-36, 14195 Berlin, Germany.
authors.forename: Max
authors.initials: M
authors.lastname: Roemer
authors.forename: Youn Kyung
authors.initials: YK
authors.lastname: Kang
authors.forename: Young Keun
authors.initials: YK
authors.lastname: Chung
authors.forename: Dieter
authors.initials: D
authors.lastname: Lentz