Organothallium compounds. VIII. Arenesulphinatodiorganothallium(III) derivatives

Abstract

The arenesulphinatodiorganothallium(~~~) complexes R2Tl(02SR') (R = Et, Me, Ph, or C6Fj ; throughout R' = Ph or p-MeC6H4) have been prepared by reaction of the appropriate diorganothallium(111) halides and silver arenesulphinates, and gave the complexes Et2(phen)T1(02SR'), impure Me2(phen)T1(02SR'), Ph2(phen or bpy)Tl- (02SR'), (C6F,)2(phen, bpy, py, or Ph3PO)T1(O2SRf), and (C6Fj)2Ph3AsOT1(02SPh) on reaction with the appropriate ligands. Attempts to prepare R2(bpy)T1(02SPh) (R = Et or Me), (C6F5)2Ph3AsOT1(02S-p-MeC&14), (C6Fj)2Ph3PTl(02SPh), and Ph2(Ph3AsO)T1(02SPh) failed. The complexes Et2T1(02SRf) are dimeric with bridging 0-sulphinate groups in chloroform, and weak association of the dimeric units is con- sidered to occur in the solid state. Conclusions are more tentative for R2T1(02SRf) (R = Me, Ph, or C6F5) derivatives, since insolubility prevented molecular weight and infrared measurements in solvents of low polarity. However, associated structures with bridging bidentate 0-sulphinate groups are likely, and sulphur-oxygen stretching frequencies suggest Me2Tl(02SR') and Ph2T1(02SR') have structures similar to Et2Tl- (02SR'). The complexes R2LT1(02SR') have monomeric structures with 0-sulphinate ligands. For L = phen or bpy, the sulphinate groups are either unidentate, giving five- coordinate thallium, or bidentate, giving six-coordinate thallium, and for L = py, Ph3P0, or Ph3As0, unidentate sulphinate groups and four-coordinate thallium are likely.