TY - JOUR
T1 - Potassium, Cesium, and Ammonium Peroxogermanates with Inorganic Hexanuclear Peroxo Bridged Germanium Anion Isolated from Aqueous Solution
AU - Medvedev, Alexander G.
AU - Mikhaylov, Alexey A.
AU - Churakov, Andrei V.
AU - Vener, Mikhail V.
AU - Tripol'skaya, Tatiana A.
AU - Cohen, Shmuel
AU - Lev, Ovadia
AU - Prikhodchenko, Petr V.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/8/17
Y1 - 2015/8/17
N2 - Potassium (K6[Ge6(μ-OO)6(μ-O)6(OH)6]·14H2O, 1), cesium ammonium (Cs4.2(NH4)1.8[Ge6(μ-OO)6(μ-O)6(OH)6]·8H2O, 2), and potassium ammonium (K2.4(NH4)3.6[Ge6(μ-OO)6(μ-O)6(OH)6]·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(μ-OO)6(μ-O)6(OH)6]6- with six μ-oxo- and six μ-peroxo groups. Peroxogermanates demonstrate relatively high thermal stability: the peroxide remains in the structure even after water release after heating to 100-120 C. DFT calculations of the peroxogermanate [Ge6(μ-OO)6(μ-O)6(OH)6]6- anion confirm its higher thermodynamic stability compared to the hydroperoxo- and oxogermanate analogues. (Chemical Equation Presented).
AB - Potassium (K6[Ge6(μ-OO)6(μ-O)6(OH)6]·14H2O, 1), cesium ammonium (Cs4.2(NH4)1.8[Ge6(μ-OO)6(μ-O)6(OH)6]·8H2O, 2), and potassium ammonium (K2.4(NH4)3.6[Ge6(μ-OO)6(μ-O)6(OH)6]·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(μ-OO)6(μ-O)6(OH)6]6- with six μ-oxo- and six μ-peroxo groups. Peroxogermanates demonstrate relatively high thermal stability: the peroxide remains in the structure even after water release after heating to 100-120 C. DFT calculations of the peroxogermanate [Ge6(μ-OO)6(μ-O)6(OH)6]6- anion confirm its higher thermodynamic stability compared to the hydroperoxo- and oxogermanate analogues. (Chemical Equation Presented).
UR - http://www.scopus.com/inward/record.url?scp=84939421956&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b01293
DO - 10.1021/acs.inorgchem.5b01293
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AN - SCOPUS:84939421956
SN - 0020-1669
VL - 54
SP - 8058
EP - 8065
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -