Item talk:Q303910

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   "abstract": "The tungstorhenate(V) heteropolyanion [W9ReO32]5-\u00a0has been isolated as guanidinium and cesium salts from reaction of [ReO2(PPh3)(py)3]+\u00a0with sodium tungstate. Crystallographic analysis of black Cs5[W9ReO32]\u00b73H2O [triclinic,\u00a0P1 or\u00a0P1\u0304;\u00a0a\u00a0= 10.194(1),\u00a0b\u00a0= 11.503(2),\u00a0c\u00a0= 9.682(1) \u00c5; \u03b1 = 100.55(1), \u03b2 = 115.81(1), \u03b3 = 99.13(1)\u00b0;\u00a0Z\u00a0= 1], based on 3743 reflections, shows the anion to be isostructural with decatungstate, [W10O32]4-. Refinement in\u00a0P1\u0304 led to reliability indices\u00a0R\u00a0= 0.084,\u00a0Rw\u00a0= 0.046. Electrochemical investigation revealed the existence of ReVI\u00a0and ReVII\u00a0analogues, 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-\u00a0and [W10O32]4-\u00a0were shown to be isomorphous by X-ray powder diffraction. Simulation of the Q-band ESR spectrum of [W9ReVIO32]4-\u00a0(polycrystalline solid solution in [W10O32]4-) gave\u00a0gx\u00a0= 1.69(1),\u00a0gy\u00a0= 1.66(1),\u00a0gz\u00a0= 1.730(2) and 104Ax(185,187Re,\u00a0I\u00a0=\u00a05/2) = (\u2212)252(10), 104Ay\u00a0= (\u2212)398(10), 104Az\u00a0= (\u2212)653(5) cm-1. The orthorhombic ESR spectrum proves that the Re atom occupies one of the eight equivalent \u201cequatorial\u201d sites in the decatungstate structure.",
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