Organothalliumhalogenide

Abstract

AbstractOrganothallium HalidesWhen TlCl3 was reacted with cHexMgCl in THF, the triorganothallane TlcHex3 (1) could be obtained. The reaction of TlCl3 with PhLi in Et2O solution at 0 °C gave after workup the insoluble colorless solid Ph2TlCl (2). 2 was refluxed in pyridine. During cooling of the hot suspension colorless small crystals of [Ph2Tl(Py)2Cl]n (3) were formed. TlMes3 and TlCl3 in the molar ration 2:1 reacted in toluene at 20 °C to give the salt (TlMes2)[MesTlCl3] (4). The treatment of TlBr with MesMgBr solution (molar ratio 2:1) in THF/toluene lead to a suspension of MesTlBr2 and Tl. The suspension was refluxed in pyridine. After cooling of the solution, colorless crystals of [MesTlBr2(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 [TlPh4]− and [Tl(Py)4]3+ units connected by Cl− ions. This would mean a description as [{TlPh4Cl}{Tl(Py)4Cl}]n. The disorder phenomena in 3 would allow the second explanation, the formation of chains [Ph2Tl(Py)2Cl]n. The unit cell of 4 contains zig‐zag chains of four‐membered rings consisting of linear (TlMes2)+ units and distorted tetrahedrons of [MesTlCl3]− ions. All chloro ligands in 4 are μ‐bridging forming Tl2Cl2 four‐membered rings and Tl‐Cl‐Tl sequences. In 5, molecular units of [MesTlBr2(Py)2] are present. The thallium atoms possess a trigonal bipyramidal environment.