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 = C₆F_s 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.