Potassium, Cesium, and Ammonium Peroxogermanates with Inorganic Hexanuclear Peroxo Bridged Germanium Anion Isolated from Aqueous Solution

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• 作者：Alexander G. Medvedev ; Alexey A. Mikhaylov ; Andrei V. Churakov ; Mikhail V. Vener ; Tatiana A. Tripol鈥檚kaya ; Shmuel Cohen ; Ovadia Lev ; Petr V. Prikhodchenko
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 17, 2015
• 年：2015
• 卷：54
• 期：16
• 页码：8058-8065
• 全文大小：495K
• ISSN：1520-510X

文摘

Potassium (K₆[Ge₆(渭-OO)₆(渭-O)₆(OH)₆]路14H₂O, 1), cesium ammonium (Cs_4.2(NH₄)_1.8[Ge₆(渭-OO)₆(渭-O)₆(OH)₆]路8H₂O, 2), and potassium ammonium (K_2.4(NH₄)_3.6[Ge₆(渭-OO)₆(渭-O)₆(OH)₆]路6H₂O, 3) peroxogermanates were isolated from 3% hydrogen peroxide aqueous solutions of the corresponding hydroxogermanates and characterized by single crystal and powder X-ray diffraction studies and by Raman spectroscopy and thermal analysis. The crystal structure of all three compounds consists of cations of potassium and/or ammonium and cesium, water molecules, and centrosymmetric hexanuclear peroxogermanate anion [Ge₆(渭-OO)₆(渭-O)₆(OH)₆]^{6鈥?/sup> with six 渭-oxo- and six 渭-peroxo groups. Peroxogermanates demonstrate relatively high thermal stability: the peroxide remains in the structure even after water release after heating to 100鈥?20 掳C. DFT calculations of the peroxogermanate [Ge₆(渭-OO)₆(渭-O)₆(OH)₆]6鈥?/sup> anion confirm its higher thermodynamic stability compared to the hydroperoxo- and oxogermanate analogues.}