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I 2400
24- 026
Solubility, Complex Formation, and Redox Reactions in the
Tl2O3—HCN/CN-—H2O System. Crystal Structures of the Cyano Compounds
Tl(CN)3·H2O, Na[Tl(CN)4]·3H2O, K[Tl(CN)4], and TlI[TlIII(CN)4] and of T lI2 C2O4.
— The dominating cyano complex of TlIII obtained by dissolution of Tl2O3 in aq. HCN
is [Tl(CN)3(aq)] as shown by 205Tl NMR. When aqueous solutions of the MCN (M: Na,
K) salts are used to dissolve Tl2O3, the equilibrium is fully shifted to the [Tl(CN)4]complex. The Tl(CN)3 and T l(CN)-4 species are synthesized for the first time in the
solid state as Tl(CN)3·H 2O (I), Tl[Tl(CN)4] (II), K[Tl(CN)4] (III), and
Na[Tl(CN)4]·3H2O (IV) salts and their structures are determined by single-crystal
XRD. (I) crystallizes in the orthorhombic space group Cmca with Z = 8, (II) and (III)
in the tetragonal space group I41/a with Z = 4, and (IV) is monoclinic, space group
C2/c, Z = 8. Along with TlIII—CN- complex formation, effective reductive dissolution
of Tl2O3 can also take place in the system yielding Tl 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 N H+4 as detected by 14 N NMR. The crystalline compounds, TlI[Tl III(CN)4], Tl 2C2O4 (monoclinic, space group P21/c, Z = 2), and
(CONH2)2 are obtained as products of such redox reactions. — (NAGY, P.; FISCHER,
A.; GLASER, J.; ILYUKHIN, A.; MALIARIK*, M.; TOTH, I.; Inorg. Chem. 44
(2005) 7, 2347-2357; Dep. Chem., Linkoeping Univ., S-581 83 Linkoeping, Swed.;
Eng.) — Schramke
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