Tungstorhenate heteropolyanions. 2. Synthesis and characterization of enneatungstorhenates(V), -(VI), and -(VII)
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Abstract
The tungstorhenate(V) heteropolyanion [W9ReO32]5- has been isolated as guanidinium and cesium salts from reaction of [ReO2(PPh3)(py)3]+ with sodium tungstate. Crystallographic analysis of black Cs5[W9ReO32]·3H2O [triclinic, P1 or P1̄; a = 10.194(1), b = 11.503(2), c = 9.682(1) Å; α = 100.55(1), β = 115.81(1), γ = 99.13(1)°; Z = 1], based on 3743 reflections, shows the anion to be isostructural with decatungstate, [W10O32]4-. Refinement in P1̄ led to reliability indices R = 0.084, Rw = 0.046. Electrochemical investigation revealed the existence of ReVI and ReVII analogues, which were hydrolytically unstable in aqueous solution but which were isolated as crystalline tetra-n-butylammonium and tetra-n-heptylammonium salts, respectively, from nonaqueous solvents. The tetra-n-butylammonium salts of [W9ReVIO32]4- and [W10O32]4- were shown to be isomorphous by X-ray powder diffraction. Simulation of the Q-band ESR spectrum of [W9ReVIO32]4- (polycrystalline solid solution in [W10O32]4-) gave gx = 1.69(1), gy = 1.66(1), gz = 1.730(2) and 104Ax(185,187Re, I = 5/2) = (−)252(10), 104Ay = (−)398(10), 104Az = (−)653(5) cm-1. The orthorhombic ESR spectrum proves that the Re atom occupies one of the eight equivalent “equatorial” sites in the decatungstate structure.
| Publication type | Article |
|---|---|
| Publication Subtype | Journal Article |
| Title | Tungstorhenate heteropolyanions. 2. Synthesis and characterization of enneatungstorhenates(V), -(VI), and -(VII) |
| Series title | Inorganic Chemistry |
| DOI | 10.1021/ic961142q |
| Volume | 36 |
| Issue | 10 |
| Year Published | 1997 |
| Language | English |
| Publisher | American Chemical Society |
| Description | 4 p. |
| First page | 2166 |
| Last page | 2169 |
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