Thallic trifluoromethanesulfonate has been prepared by reaction of trifluoromethanesulfonic acid
with either thallic oxide or solutions of thallic trifluoroacetate in trifluoroacetic acid, and has been
isolated as the trihydrate on crystallization fromnitromethane. The polyfluoroarenes,p-CH3OC6F4H,
p-CH3C6F4H, m-H2C6F4, o-H2C6F4, p-H2C6F4, C6F5H, 1,3,5-F3C6H3 or 1,2,4-F3C6H3, have been
thallated by thallic trifluoromethanesulfonate in trifluoroacetic acid, giving the corresponding poly-
fluorophenylthallium(III) bis(trifluoromethanesulfonates), which have been characterized spectroscopically and by conversion into the corresponding (polyfluoro)iodobenzenes on treatment with sodium
iodide. Only slight thallation of m-BrC6F4H and m-O2NC6F4H was observed. By contrast with
thallic trifluoromethanesulfonate, thallic trifluoroacetate in trifluoroacetic acid induced little thallation
of the most reactive polyfluorobenzene, p-CH3OC6F4H. Thallic trifluoromethanesulfonate also
thallated p-CH3OC6F4H in nitromethane, sulfolane, and with the substrate as solvent, but
p-CH3C6F4H failed to react. Treatment of the polyfluorophenylthallium(III) bis(trifluoromethane-
sulfonates) with boiling aqueous sodium acetate caused symmetrization into the corresponding
acetatobis(polyfluorophenyl)thallium(III) compounds. A similar reaction between 2,4,6-trifluoro-
phenylthallium(III) bis(trifluoromethanesulfonate) and sodium acetate at room temperature yielded
2,4,6-trifluorophenylthallium(III) diacetate. 2,3,4,6-Tetrafluorophenylthallium(III) bis(trifluor0-
methanesulfonate) was converted by boiling water into bis(2,3,4,6-tetrafluorophenyl)thallium(III)
trifluoromethanesulfonate.