13453-32-2Relevant articles and documents
Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution
Blixt, Johan,Glaser, Julius,Mink, Jànos,Persson, Ingmar,Persson, Per,Sandstr?m, Magnus
, p. 5089 - 5104 (1995)
The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlXn(OH2)m](3-n)+, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH2)63+, TlX(OH2)52+, and trans-TlX2(OH2)4+. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr3(OH2)2 complex and possibly also for TlCl3(OH2)2. The TlX4- complexes are all tetrahedral. Higher chloride complexes, TlCl5(OH2)2- and TlCl63-, are formed and have again octahedral coordination geometry. For the first and second halide complexes, TlX(OH2)52+ and TlX2(OH2)4+, no lengthening was found of the Tl-X bonds, with Tl-Br distances of 2.50(2) and 2.49(2) ?, respectively, and Tl-Cl distances of 2.37(2) ? for both complexes. The mean Tl-O bond distances increase slightly, ≈0.04 ?, from that of the Tl(OH2)63+ ion, at the formation of the first thallium(III) halide complexes. A further, more pronounced lengthening of about 0.1 ? occurs when the second complex forms, and it can be related to the relatively high bond strength in the trans-XTlX entity, which also is manifested through the Tl-X stretching force constants. For the recently established Tl(CN)n(3-n)+ complexes with no previously available structural information, the Tl-C distances were determined to be 2.11(2), 2.15(2), and 2.19-(2) ? for n = 2, 3, and 4, respectively. The Tl(CN)2+ complex has a linear structure, and the Tl(CN)4- complex is tetrahedral with the CN- ligands linearly coordinated. The lower complexes (n = 1-3) are hydrated, although the coordination numbers could not be unambiguously determined. A well-defined second coordination sphere corresponding to at least eight water molecules at a Tl-OII distance of ≈4.3 ? was found around the second complex, probably trans-Tl(CN)2(OH2)4+. The third cyano complex is probably pseudotetrahedral, Tl(CN)3(OH2). The bonding in the hexahydrated Tl3+ and Hg2+ ions is discussed, and differences in the mean M-O bond lengths, determined by the LAXS and EXAFS techniques, are interpreted as being due to an occurrence of two different sets of M-O distances in the first hydration shell.
Formation, equilibrium properties and decomposition in aqueous solution of monoorganothallium(III) ions containing RC(O)CH2 groups. Preparation of monoacetonylthallium(III) compounds
Gyoeri, Bela,Sanchez, Augustin,Glaser, Julius
, p. 1 - 16 (1989)
The reactions of thallium(III) with some ketones in the presence and absence of Cl-, Br-, CN-, CH3COO-, and CF3COO- ions in acidic aqueous solutions, and the stabilities of the resulting monoorganotha
Organothallium halides
Kuzu, Istemi,Neumueller, Bernhard
, p. 1524 - 1530 (2008/10/09)
When 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. I 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 4Cl}{Tl(Py)4CI}]n. The disorder phenomena in 3 would allow the second explanation, the formation of chains [Ph 2Tl(Py)2Cl]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 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.
