Search: onr:"swepub:oai:DiVA.org:liu-45469" >
Solubility, complex...
Solubility, complex formation, and redox reactions in the Tl 2O3-HCN/CN--H2O system. Crystal structures of the cyano compounds Tl(CN)3·H2O, Na[Tl(CN)4]·3H2O, K[Tl(CN)4], and TlITlIII(CN)4 and of TlI2C2O
-
- Nagy, P. (author)
- Dept. of Inorg. and Analyt. Chem., University of Debrecen, Pf. 21, H-4010 Debrecen, Hungary
-
- Fischer, A. (author)
- Department of Chemistry, Inorganic Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden
-
- Glaser, J. (author)
- Department of Chemistry, Inorganic Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden
-
show more...
-
- Ilyukhin, A. (author)
- Kurnakov Inst. of Gen./Inorg. Chem., Russian Academy of Sciences, Leninsky Prospect 31, 119 991 Moscow, Russian Federation
-
- Maliarik, Mikhail (author)
- Linköpings universitet,Tekniska högskolan,Institutionen för fysik, kemi och biologi
-
- Toth, I. (author)
- Tóth, I., Dept. of Inorg. and Analyt. Chem., University of Debrecen, Pf. 21, H-4010 Debrecen, Hungary
-
show less...
-
Dept of Inorg. and Analyt. Chem., University of Debrecen, Pf. 21, H-4010 Debrecen, Hungary Department of Chemistry, Inorganic Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden (creator_code:org_t)
- 2005-03-08
- 2005
- English.
-
In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 44:7, s. 2347-2357
- Related links:
-
https://urn.kb.se/re...
-
show more...
-
https://doi.org/10.1...
-
show less...
Abstract
Subject headings
Close
- Thallium(III) oxide can be dissolved in water in the presence of strongly complexing cyanide ions. TlIII 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 Tl 2O3 in HCN is [Tl(CN)3(Bq)] as shown by 205Tl NMR. The Tl(CN)3 species has been selectively extracted into diethyl ether from aqueous solution with the ratio CN -/TlIII = = 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 [Tl(CN) 4]- complex. The Tl(CN)3 and Tl(CN) 4- species have for the first time been synthesized in the solid state as Tl(CN)3·H2O (1), M[Tl(CN) 4] (M = Tl (2) and K (3)), and Na[Tl(CN)4]·3H 2O (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-Tl-N fragment. In the three compounds of the tetracyano-thallium(III) complex, 2-4, the [Tl(CN)4]- unit has a distorted tetrahedral geometry. Along with the acidic leaching (enhanced by TlIII-CN- complex formation), an effective reductive dissolution of the thallium(III) oxide can also take place in the Tl 2O3-HCN-H2O system yielding thallium(I), 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 14N NMR. The crystalline compounds, TlI[Tl III(CN)4], TlI2C2O 4, and (CONH2)2, have been obtained as products of the redox reactions in the system. © 2005 American Chemical Society.
Keyword
- TECHNOLOGY
- TEKNIKVETENSKAP
Publication and Content Type
- ref (subject category)
- art (subject category)
Find in a library
To the university's database