- Thallium(III) complexes of the metalloligands [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-Se)2(PPh3)4]
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Reactions of [Pt2(μ-S)2(PPh3)4] with the diarylthallium(III) bromides Ar2TlBr [Ar = Ph and p-ClC6H4] in methanol gave good yields of the thallium(III) adducts [Pt2(μ-S)2(PPh3)4TlAr2]+, isolated as their BPh4- salts. The corresponding selenide complex [Pt2(μ-Se)2(PPh3)4TlPh2]BPh4 was similarly synthesised from [Pt2(μ-Se)2(PPh3)4], Ph2TlBr and NaBPh4. The reaction of [Pt2(μ-S)2(PPh3)4] with PhTlBr2 gave [Pt2(μ-S)2(PPh3)4TlBrPh]+, while reaction with TlBr3 gave the dibromothallium(III) adduct [Pt2(μ-S)2(PPh3)4TlBr2]+[TlBr4]-. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt2(μ-S)2(PPh3)4TlPh2]BPh4, [Pt2(μ-S)2(PPh3)4TlBrPh]BPh4 and [Pt2(μ-S)2(PPh3)4TlBr2][TlBr4] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.
- Rose, Sarah L.,Henderson, William,Nicholson, Brian K.,Hor, T.S. Andy
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p. 5237 - 5244
(2010/05/01)
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- Diphenylthallium(III) thiosemicarbazonates: Flexibility of coordination in the solid state and polymorphism in chloroform solution
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The reactions of diphenylthallium(III) hydroxide in water-ethanol at room temperature with thiosemicarbazones HL=R=N(3)-N(2)H-C(1)(S)-N(1)H2 (RO=cyclopentanone, benzaldehyde, 2-hydroxybenzaldehyde, 4-methoxybenzaldehyde, acetophenone, furan-2-carbaldehyde, pyridine-2-formaldehyde and pyridine-2-acetaldehyde) afforded novel diphenylthallium(III) thiosemicarbazonates of stoichiometry [TlPh2(L)] (compounds 1-8, respectively) that were characterised with the help of analytical data, physical properties, IR spectrometry, multinuclear (1H, 13C and 205Tl) NMR spectroscopy and X-ray studies of 1, 7 and 8. In crystals of 1 (and probably also in those of 2, 4, 5 and 6), Tl(III) is bound to two phenyl carbons and to the N(3) and S atoms of the monodeprotonated thiosemicarbazone in a distorted trigonal bipyramidal coordination polyhedron with one vacant site in the equatorial plane. In 3 the metal atom is S,N(3),O-coordinated. In 7 and 8 there are three independent molecules: all three have distorted trigonal bipyramidal coordination with Tl coordinated to two carbon atoms and to the N(Py), N(3) and S atoms of the deprotonated thiosemicarbazones, but they differ significantly in their bonding parameters. The 205Tl NMR spectra suggest that for 1-6 more than one coordination mode is present in solution in chloroform, whereas for 7 and 8 there is only one species. Low temperature proton NMR studies of 7 and 8 showed that the energy barrier to rotation of the amino groups about the C1-N1 bond correlated with the bonding parameters of the thioamide group in the solid state; in both cases the barrier is somewhat higher than in thiosemicarbazonates of PhHg(II).
- Lobana, Tarlok S.,Casas, José S.,Casti?eiras, Alfonso,García-Tasende, María S.,Sánchez, Agustín,Sordo, José
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- Synthesis of Diphenylthallium Acetate and Bromide from Phenylhydrazine and Thallium(III) Oxide
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A new procedure for synthesis of diphenylthallium acetate and bromide was developed, involving reaction of phenylhydrazine with thallium(III) oxide to give organothallium compounds. Certain factors affecting this reaction were studied.
- Gun'kin
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