Voltammetric Reduction of α- and γ*-[S2W18O62]4- and α-, β-, and γ-[SiW12O40]4-: Isomeric Dependence of Reversible Potentials of Polyoxometalate Anions Using Data Obtained by Novel Dissolution and Conventional Solution-Phase Processes
| Autor: | Jie Zhang, Alan M. Bond, Peter J. S. Richardt, Anthony G. Wedd |
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| Rok vydání: | 2004 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 43:8263-8271 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | Comparative studies on the voltammetric reduction of the α and γ* isomers of Dawson [S2W18O62]4- and α, β, and γ forms of Keggin [SiW12O40]4- polyoxometalate anions have been undertaken. For the six reversible one-electron [S2W18O62]4-/5-/6-/7-/8-/9-/10- processes in acetonitrile, reversible potentials (E0‘) were found to be independent of isomeric form within experimental error (±5 mV). However, because both the α and γ* isomers of [Bu4N]4[S2W18O62] are insoluble in water, solid-state voltammetric studies with microcrystals adhered to electrode surfaces in contact with aqueous Et4NCl and Bu4NCl electrolyte media were also possible. Although no isomeric distinction was again detected in the solid-state studies, it was found that reduction of adhered solid by four or more electron equivalents led to rapid dissolution. When Et4NCl was the electrolyte, this dissolution process coupled with potential cycling experiments enabled conventional solution-phase data to be obtained in water for the analogous six one... |
| Databáze: | OpenAIRE |
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