New Compounds Bearing [M(S2O7)(3)](2-) Anions (M=Si, Ge, Sn): Syntheses and Characterization of A(2)[Si(S2O7)(3)] (A=Na, K, Rb), A(2)[Ge(S2O7)(3)] (A=Li, Na, K, Rb, Cs), A(2)[Sn(S2O7)(3)] (A=Na, K), and the Unique Germanate Hg-2[Ge(S2O7)(3)]Cl-2 with Cationic 1 infinity[HgCl2/2](+) Chains

作者：Logemann Christian; Witt Julia; Gunzelmann Daniel; Senker Juergen; Wickleder Mathias S^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2012, 638(12-13): 2053-2061.

DOI：10.1002/zaac.201200343

• Metallates
• Disulfates
• Mercury
• Crystal structure
• Thermal behavior

The reaction of the group 14 tetrachlorides MCl4 (M = Si, Ge, Sn) with oleum (65?% SO3) at elevated temperatures led to the unique anionic complexes [M(S2O7)3]2 that show the central M atoms in coordination of three chelating S2O72 groups. The mean distances MO within the complexes increase from 175 pm (M = Si) via 186 pm (M = Ge) up to 200 pm (M = Sn). The charge balance for the [M(S2O7)3]2 anions is achieved by alkaline metal ions A+ (A = Li, Na, K, Rb, Cs) which were implemented in the syntheses in form of their sulfates. The size of the A+ ions, i.e. their coordination requirement causes the crystallographic differences in the crystal structures, while the structure of the complex [M(S2O7)3]2 anions remains essentially unaffected. Furthermore, we were able to characterize the unique germanate Hg2[Ge(S2O7)3]Cl2 which forms when HgCl2 is added as a source for the counter cation. The Hg2+ and the Cl ions form infinite cationic chains according to 18[HgCl2/2]+ which take care for the charge compensation. For selected examples of the compounds the thermal behavior has been monitored by means of thermal analyses and X-ray powder diffraction. For A being an alkaline metal the decomposition product is a mixture of the sulfates A2SO4 and the dioxides MO2, whereas Hg2[Ge(S2O7)3]Cl2 shows a more complicated decomposition. The tris-(disulfato)-silicate Na2[Si(S2O7)3] has additionally been examined by solid state 29Si and 23Na NMR spectroscopic measurements.

• 出版日期2012-10