Cation-Directed Synthesis of Tungstosilicates. 2. Synthesis, Structure, and Characterization of the Open Wells−Dawson Anion α-[{K(H2O)2}(Si2W18O66)]15-and Its Transiton-Metal Derivatives [{M(H2O)}(μ-H2O)2K(Si2W18O66)]13-and [{M(H2O)}(μ-H2O)2K{M(H2O)4}(Si2W18O66)]11
| Autor: | Nathalie Leclerc-Laronze, Jérôme Marrot, Gilbert Herve |
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| Rok vydání: | 2005 |
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| Zdroj: | Inorganic Chemistry. 44:1275-1281 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic0486769 |
| Popis: | The dimer α-[{K(H2O)2}(Si2W18O66)]15- (1), synthesized by reacting K10A-α-[SiW9O34] with two equivalents of H+ in aqueous solution, has been characterized by polarography and 183W NMR spectroscopy. Nine resonance signals have been observed with the tetrabutylammonium salt in dimethylformamide/acetonitrile solution, in agreement with the crystal structure of the anion which consists of two A-α-[SiW9O34]10- associated through two W−O−W junctions. This anion derives from the Wells−Dawson structure by breaking four W−O−W junctions. The pocket between the two-half-anions can be filled by several metal cations. Reaction of transition-metal cations with 1 leads to the formation of [{M(H2O)}(μ-H2O)2K(Si2W18O66)]13- (1M) (M = Co, Ni, Cu) and [{M(H2O)}(μ-H2O)2K{M(H2O)4}(Si2W18O66)]11- (1M2) (M = Mn, Co, Ni) complexes. One potassium is always included in the pocket with one or two transition metals. Because of the shift of the potassium cation to one side of the anion, the coordination modes of the two transition me... |
| Databáze: | OpenAIRE |
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