Organothallium compounds. XI. Reactions of thallic salts with some sodium arenesulphinates

Desulphination reactions between sodium mesitylenesulphinate and the thallic salts TlX₃ (X = MeCO₂, CF₃CO₂ or Cl) in aqueous acetic acid or water gave mesitylthallium(III) diacetate or the complexes RTl(O₂SR)X (R = 2,4,6-Me₃C₆H₂; X = MeCO₂ or Cl) at room temperature and dimesitylthallium(III) mesitylenesulphinate at 100°C. The diacetate was independently synthesized by metathesis from mesitylthallium(III) dichloride, and was converted into RTl(O₂SR)O₂CMe by sodium mesitylenesulphinate. The derivatives RTl(O₂SR)X gave mesitylthallium(III) dichloride on treatment with HCl and rearranged into dimesitylthallium mesitylenesulphinate in boiling aqueous acetic acid or water. Thermal decomposition of RTl(O₂SR)O₂CMe under vacuum yielded dimesitylthallium(III) acetate. The structures of the mesitylthallium sulphinate and acetate complexes are discussed. Reaction of thallic acetate or trifluoroacetate with sodium 2,4,6-triisopropylbenzenesulphinate in aqueous acetic acid gave Tl^I[Tl^III(O₂SR¹)₄ ] [R¹ = 2,4,6-(Me₂CH)₃C₆H₂] at room temperature and the thiosulphonate R¹SO₂SR¹ at 100°C, whilst reactions with sodium benzenesulphinate and p-toluenesulphinate gave the diaryl disulphones.