One-electron reduction of the γ*-isomer of [S2W18O62]4 leads to isolation of the α-isomer
| Autor: | Jonathon M. White, Peter A. Tregloan, Alan M. Bond, Peter J. S. Richardt, Anthony G. Wedd |
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| Rok vydání: | 2001 |
| Předmět: | |
| Zdroj: | Canadian Journal of Chemistry. 79:613-620 |
| ISSN: | 1480-3291 0008-4042 |
| Popis: | Bu4N+ salts of [S2W18O62]5 and [S2W18O62]6 can be isolated by electro reduction of γ*-(Bu4N)4[S2W18O62] in MeCN. α-(Bu4N)5[S2W18O62]·4MeCN crystallizes in space group C2/c with a = 26.226(2) Å, b = 15.570(2) Å, c = 38.407(2) Å, β = 115.59(2)°, V = 14 145(2) Å3, and Z = 8. The observations indicate that a γ* « α isomerization is associated with the [S2W18O62]4 [S2W18O62]5 couple. However, the transformation could not be detected on the timescale of cyclic voltammetry up to a scan rate of 10 V s1. The available data suggest that either: (i) the γ* « α equilibrium favors one of the isomers in solution for both redox states, or (ii) the isomerization is slow on the cyclic voltammetric timescale but the differences in E1/2 values for the α-[S2W18O62]4[S2W18O62]5 and γ*-[S2W18O62]4[S2W18O62]5 couples cannot be resolved by cyclic voltammetry.Key words: polyoxometalates, synthesis, electrochemistry, isomerization. |
| Databáze: | OpenAIRE |
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