Synthesis, Crystal Structure, and Electrochemistry of Mono- and Bis-Homoannular Ferrocene Derivatives

Abstract

Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1′,2′-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel–Crafts acylation of ferrocene using succinic anhydride gave mono- or bis(3-carboxypropinoyl)-ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1′,2′-bis(α-ketotetramethylene)-ferrocene. The diastereomeric mixture of the latter diketones was separated using column chromatography, characterized via single-crystal X-ray analysis, and assigned its stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene)-ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges.

Keywords

• 1,2-(α-ketotetramethylene)-ferrocene
• 1,2-(tetramethylene)-ferrocene
• ferrocene
• Friedel–Crafts acylation
• Clemmensen reduction
• X-ray crystallography