Das erste KEGGIN-Anion mit tetraedrischer. Kupfer(II)—Sauerstoff-Koordination: [α-Cu0,4(H2)0,6O4W12O36]6− |
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Authors: | H-J Lunk S Giese J Fuchs R Stsser |
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Institution: | H.-J. Lunk,S. Giese,J. Fuchs,R. Stösser |
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Abstract: | The First KEGGIN-Anion with Tetrahedral Coordination of Copper(II)-Oxygen: α-Cu0,4(H2)0.6O4W12O36]6? The solution of the CuII-containing heteropolyanion was prepared starting from an aqueous solution of Na2WO4, adjusting to pH 5–6 by adding slowly a solution of Cu(NO3)2 in HNO3. The addition of the corresponding amount of N(CH3)4Br to the concentrated solution led to the crystallization of the greenish-yellow mixed crystals (TMA)6α-Cu0.4(H2)0.6O4W12O36] · 9 H2O. After repeated recrystallization it has been investigated by chemical, spectroscopic (IR/Raman, UV, 183W/1H-NMR, ESR) and X-ray diffraction methods (monoclinic; space group P21; a = 13.117(4), b = 21.466(4), c = 13.223(3) Å, β = 91.60°; Z = 2; Dc = 3.041 g · cm?3; R = 8.0%). The distances of the four “tetrahedral” oxygen atoms to the position (0, 0, 0) range from 1.67 to 1.93 Å. The alternative occupation of the central KEGGIN position with copper(II) and two protons, respectively, accounts for the different distances. The prepared solid solution represents the first example for the tetrahedral copper(II)-oxygen coordination in any heteropolyanion compound. |
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Keywords: | CuII heteropolyanion tetrahedral copper(II)-oxygen coordination IR Raman UV 183W/1H NMR ESR data crystal structure |
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