The Unprecedented Tetrakis-(disulfato)-silicate Anion [Si(S2O7)4]4−, its Germanium Congener [Ge(S2O7)4]4−, and the Tris-(disulfato)-metallates [M(S2O7)3]2− (M=Si, Ge, Ti), Stabilized by Divalent Counter Cations B2+ (B=Sr, Ba, Pb)

Authors

  • Dipl. Chem. Christian Logemann,

    1. Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry, Carl-von-Ossietzky-Strasse 9–11, 26129 Oldenburg (Germany), Fax: (+49) 441-798 3352
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  • Dr. Katja Rieß,

    1. Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry, Carl-von-Ossietzky-Strasse 9–11, 26129 Oldenburg (Germany), Fax: (+49) 441-798 3352
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  • Prof. Dr. Mathias S. Wickleder

    Corresponding author
    1. Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry, Carl-von-Ossietzky-Strasse 9–11, 26129 Oldenburg (Germany), Fax: (+49) 441-798 3352
    • Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry, Carl-von-Ossietzky-Strasse 9–11, 26129 Oldenburg (Germany), Fax: (+49) 441-798 3352

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Abstract

The reaction of oleum (65 % SO3) with the tetrachlorides of silicon, germanium, and titanium, respectively, led to the complex disulfates Sr2[M(S2O7)4] (M=Si, Ge), Ba[M(S2O7)3] (M=Si, Ge, Ti) and Pb[M(S2O7)3] (M=Ge, Ti) if strontium, barium, and lead were used as divalent counter cations. The strontium compounds exhibit the unique tetrakis-(disulfato)-metallate anions [M(S2O7)4]4− with the silicon and germanium atoms in octahedral coordination of two chelating and two monodentate disulfate groups. All of the other compounds display tris-(disulfato)-metallate anions [M(S2O7)3]2− with three chelating disulfate groups surrounding the M atoms. Thermoanalytical investigations on the germanium compounds Sr2[Ge(S2O7)4] and Ba[Ge(S2O7)3] revealed their decomposition in multi-step processes leading to a mixture of BSO4 and BGe4O9 (B=Sr, Ba), while the thermal degradation of Pb[Ti(S2O7)3] yields PbTiO3. For selected examples, IR data are additionally presented.

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