Organothalliumhalogenide

Organothallium Halides When TlCl 3 was reacted with c HexMgCl in THF, the triorganothallane Tl c Hex 3 ( 1 ) could be obtained. The reaction of TlCl 3 with PhLi in Et 2 O solution at 0 °C gave after workup the insoluble colorless solid Ph 2 TlCl ( 2 ). 2 was refluxed in pyridine. During cooling of the hot suspension colorless small crystals of [Ph 2 Tl(Py) 2 Cl] n ( 3 ) were formed. TlMes 3 and TlCl 3 in the molar ration 2:1 reacted in toluene at 20 °C to give the salt (TlMes 2 )[MesTlCl 3 ] ( 4 ). The treatment of TlBr with MesMgBr solution (molar ratio 2:1) in THF/toluene lead to a suspension of MesTlBr 2 and Tl. The suspension was refluxed in pyridine. After cooling of the solution, colorless crystals of [MesTlBr 2 (Py) 2 ]·Py ( 5 ) could be isolated. 1 and 3 – 5 were characterized by NMR and MS techniques and in the case of 3 by vibrational spectroscopy. In addition X‐ray structure determinations of 3 ‐ 5 were performed. According to this the structure of 3 can be understood in two ways: 3 consists of polymeric linear chains along [001] buildt‐up by square planar [TlPh 4 ] − and [Tl(Py) 4 ] 3+ units connected by Cl − ions. This would mean a description as [{TlPh 4 Cl}{Tl(Py) 4 Cl}] n . The disorder phenomena in 3 would allow the second explanation, the formation of chains [Ph 2 Tl(Py) 2 Cl] n . The unit cell of 4 contains zig‐zag chains of four‐membered rings consisting of linear (TlMes 2 ) + units and distorted tetrahedrons of [MesTlCl 3 ] − ions. All chloro ligands in 4 are μ‐bridging forming Tl 2 Cl 2 four‐membered rings and Tl‐Cl‐Tl sequences. In 5 , molecular units of [MesTlBr 2 (Py) 2 ] are present. The thallium atoms possess a trigonal bipyramidal environment.