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Solubility, complex formation, and redox reactions in the Tl2O3-HCN/CN--H2O system. Crystal structures of the cyano compounds Tl(CN)(3)center dot H2O, Na Tl(CN)(4) center dot 3H(2)O, K Tl(CN)41, and Tl-I Tl-III(CN)41 and of (Tl2C2O4)-C-I
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
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2005 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, no 7, p. 2347-2357Article in journal (Refereed) Published
Abstract [en]

Thallium(III) oxide can be dissolved in water in the presence of strongly complexing cyanide ions. TI111 is leached from its oxide both by aqueous solutions of hydrogen cyanide and by alkali-metal cyanides. The dominating cyano complex of thallium(III) obtained by dissolution of TI2O3 in HCN is [TI(CN)(3)(aq)] as shown by (TI)-T-205 NMR. The TI(CN)(3) species has been selectively extracted into diethyl ether from aqueous solution with the ratio CN-/TI111 = 3. When aqueous solutions of the MCN (M = Na+, K+) salts are used to dissolve thallium(III) oxide, the equilibrium in liquid phase is fully shifted to the [TI(CN)(4)](-) complex. The TI(CN)(3) and TI(CN)(4)(-) species have for the first time been synthesized in the solid state as TI(CN)(3)(H2O)-H-. (1), M[TI(CN)(4)] (M = TI (2) and K (3)), and Na[TI(CN)(4)](.)3H(2)O (4) salts, and their structures have been determined by single-crystal X-ray diffraction. In the crystal structure of 1, the thallium(III) ion has a trigonal bipyramidal coordination with three cyanide ions in the equatorial plane, while an oxygen atom of the water molecule and a nitrogen atom from a cyanide ligand, attached to a neighboring thallium complex, form a linear O-TI-N fragment. In the three compounds of the tetracyano-thallium(III) complex, 2-4, the [TI(CN)(4)](-) unit has a distorted tetrahedral geometry. Along with the acidic leaching (enhanced by TI111-CN- complex formation), an effective reductive dissolution of the thallium(III) oxide can also take place in the TI2O3-HCN-H2O system yielding thallium(l), while hydrogen cyanide is oxidized to cyanogen. The latter is hydrolyzed in aqueous solution giving rise to a number of products including (CONH2)(2), NCO-, and NH4+ detected by N-14 NMR. The crystalline compounds, TI1[TI111(CN)(4)], (TI2C2O4)-C-1, and (CONH2)(2), have been obtained as products of the redox reactions in the system.

Place, publisher, year, edition, pages
2005. Vol. 44, no 7, p. 2347-2357
Keyword [en]
potassium tetroxalate, molecular-structure, aqueous-solution, nmr, thallium(iii), perchlorate, diffraction, chloride, bromide, c-13
Identifiers
URN: urn:nbn:se:kth:diva-14648DOI: 10.1021/ic0485918ISI: 000228054200030Scopus ID: 2-s2.0-16344384019OAI: oai:DiVA.org:kth-14648DiVA, id: diva2:332689
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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