Organothallium Compounds. XVI. Formation of Tris(polyfluorophenyl)thallium(III) Compounds by Reaction of Bromobis(polyfluorophenyl) thallium(III) Compounds with Metal Polyfluorobenzenesulfinates

Abstract

The tris(polyfluorophenyl)thallium(III) compounds R3Tl (R = C6F5, p-HC6F4 or o-HC6F4) have been obtained by reaction of bromobis(polyfluorophenyl) thallium(III) compounds with the corresponding barium (R = C6Fs or p-HC6F4) or thallium(1) (R = o-HC6F4) polyfluorobenezensulfinates in boiling pyridine, and have been isolated as the complexes R,Tl(diox) (diox = 1,4-dioxan). The reactions are considered to proceed by formation and desulfination of polyfluorobenzenesulfinatobis (polyfluorophenyl)thallium(III) intermediates. Sulfur dioxide elimination has also been observed on reaction of (p-HC6F4)2TlBr with barium bis(pentafluorobenzenesulfinate). The barium sulfinates were prepared by metathesis from the corresponding lithium salts and underwent little decomposition in boiling pyridine. Thallium(1) 2,3,4,5-tetrafluorobenzenesulfinate was obtained by neutralization of the corresponding sulfinic acid with thallium(I) hydroxide, and decomposed into thallium(I) sulfate, bis(2,3,4,5-tetrafluorophenyl) sulfide, bis(2,3,4,5-tetrafluorophenyl) disulfide and 1,2,3,4-tetrafluorobenzene in boiling pyridine. Desulfination occurred on reaction of silver nitrate with lithium pentafluorobenzenesulfinate in water giving silver sulfite and pentafluorobenzene.