The mono- and bis-(trichloroacetic acid)-solvates of ferricenium trichloroacetate

Summary Inconsistent literature reports on the preparation of the mono- and bis-(trichloroacetic acid)-solvated ferricenium trichloroacetates, (1) and (2) have prompted a comprehensive investigation of the experimental conditions giving rise to the formation of the two ferricenium salts. In agreement with the majority of authors, (2) is reproducibly obtained from trichloroacetic acid and ferrocene in molar ratios of 3 and higher in benzene over a wide range of experimental variables in the presence of air or, preferably, under conditions of oxygen saturation. Treatment of aqueous ferricenium sulfate solutions with trichloroacetic acid in an acid/ferrocene ratio of 3 and above affords the di-solvate, whereas at lower reactant ratios, and under conditions of reduced acidity, formation of the mono-solvate prevails. More efficiently, and in a higher degree of purity, the latter salt is generated from the former by a controlled recrystallization from water. Representative spectroscopic features of the two salts are discussed.