
%0 Journal Article
%A Deacon, GB 
%A Phillips, RJ 
%T Organothallium compounds. XIV. Thermal decomposition of some Polyfluorobenzoatobis(polyfluorophenyl)thallium(III) compounds
%J Australian Journal of Chemistry
%D 1978/08/01
%V 31
%N 8
%P 1709-1724
%K 
%R https://doi.org/10.1071/CH9781709
%U https://www.publish.csiro.au/paper/CH9781709 
%X The organothallium carboxylates, R2TIO2CR (R = C6F5, p-MeOC6F4, p-HC6F4, m-HC6F4 or o-HC6F4), prepared by reactions of appropriate halogenobis(polyfluorophenyl)thallium(III) compounds and sodium carboxylates, are considered to have associated structures with bridging carboxylate groups. Thermal decomposition of R2TlO2CR (R = C6F5, p-MeOC6F4 or p-HC6F4 or m-HC6F4) in boiling pyridine resulted in decarboxylation and formation of the corresponding tris(polyfluorophenyl)thallium compounds, which were isolated in analytically pure form as the complexes R3Tl(diox) (R = C6F5, p-HC6F4 or m-HC6F4; diox = 1,4-dioxan) and R3Tl(bpy) (R = C6F5 or p-MeOC6F4; bpy = 4,4'-bipyridyl). However, no decomposition was observed when R = o-HC6F4. The ease of decarboxylation decreased in the sequence R = C6F5 > p-MeOC6F5 &#8805; p-HC6F4 &#8776; m-HC6F4 S o-HC6F4, and a possible mechanism is discussed. Pyrolysis of R2TIO2CR (R = C6F5, p-MeOC6F4, p-HC6F4, m-HC6F4 or o-HC6F4) at 310&#176; under nitrogen in the absence of a solvent gave tris(polyfluorophenyl)thallium compounds (R = C6F5, p-MeOC6F4, p-HC6F4 or m-HC6F4), isolated as the dioxan complexes, thallous fluoride and polyfluorobiphenyls and polyfluoropolyphenyls. In addition, decafluorobenzophenone was obtained when R = C6F5, methyl fluoride when R = p-MeOC6F4 and the corresponding tetrafluorobenzene C6H2F4 when R = p-HC6F4, m-HC6F4 or o-HC6F4. Chlorobis(2,3,5,6-tetrafluoro-4-methoxyphenyl)thallium(III) was prepared by reaction of thallic chloride with 2,3,5,6-tetrafluoro-4-methoxyphenyllithium, which was obtained from 2,3,5,6-tetra- fluoroanisole and butyllithium. 
