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Australian Journal of Chemistry Australian Journal of Chemistry Society
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RESEARCH ARTICLE

Organothallium compounds. XIV. Thermal decomposition of some Polyfluorobenzoatobis(polyfluorophenyl)thallium(III) compounds

GB Deacon and RJ Phillips

Australian Journal of Chemistry 31(8) 1709 - 1724
Published: 1978

Abstract

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 ≥ p-HC6F4 ≈ 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° 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.

https://doi.org/10.1071/CH9781709

© CSIRO 1978

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