Wade L. Davis, R. F. Shago, E. Langner
Aug 25, 2005
Citations
0
Influential Citations
51
Citations
Journal
Polyhedron
Abstract
Abstract A series of primary ferrocenylalcohols, Fc–(CH2)m–OH with m = 1–4 and Fc = ferrocenyl, was synthesised by reduction of the appropriate ferrocenylcarboxylic acids, Fc–(CH2)n–COOH (n = 0–3) and the ester methyl 4-ferrocenylbutanoate with LiAlH4, the reduction of the γ-ketoacid ferrocylpropanoic acid, Fc–CO–(CH2)2–COOH, with AlCl3/LiAlH4, and the reduction of ferrocenylcarboxaldehyde, FcCHO, with NaBH4. The secondary ferrocenyl alcohols CpFe(C5H4–CH(OH)–CH3) and Fe(C5H4–CH(OH)–CH3)2 were obtained by NaBH4 reduction of acetyl and diacetyl ferrocene. The different reduction methods are compared. The electrochemistry of the alcohols was studied by cyclic voltammetry in CH3CN/0.1 M N(nBu)4PF6 utilising a platinum working electrode. The ferrocenyl group showed reversible electrochemistry with the formal reduction potential (Eo′ versus Fc/Fc+) of the ferrocenyl group inversely proportional to side chain length. The influence of the side chain length on Eo′ was more pronounced for the acids because the electron-withdrawing properties of the carbonyl group is stronger than that of the alcohol group. Ion pairing was found to play a major role in the electrochemical behaviour of ferrocenylmethanol, Fc–CH2–OH.