Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)

Logemann, Christian, Gunzelmann, Daniel, Kluner, Thorsten, Senker, Jurgen and Wickleder, Mathias S. 2012, Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag), Chemistry : a European journal, vol. 18, no. 48, pp. 15495-15503, doi: 10.1002/chem.201202344.

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Title Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)
Author(s) Logemann, Christian
Gunzelmann, Daniel
Kluner, Thorsten
Senker, Jurgen
Wickleder, Mathias S.
Journal name Chemistry : a European journal
Volume number 18
Issue number 48
Start page 15495
End page 15503
Total pages 9
Publisher Wiley
Place of publication London, Eng.
Publication date 2012-11-26
ISSN 1521-3765
Keyword(s) density functional calculations
NMR spectroscopy
thermal decomposition
vibrational spectroscopy
Summary The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2−, which show the central M atoms in coordination with three chelating S2O72− groups. The mean distances M[BOND]O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M[BOND]O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid-state NMR measurements have been performed, with the results showing a signal at −215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2− ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2− ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements.
Language eng
DOI 10.1002/chem.201202344
Field of Research 039999 Chemical Sciences not elsewhere classified
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2012, Wiley
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