Solvation Effect of Li+ on the Voltammetric Properties of [PMo12O40]3−. Part 2: Comparative Studies on the Preferential Solvation in Acetonitrile+S and Acetone+S Mixtures
✍ Scribed by Sadayuki Himeno; Masayo Takamoto; Tadaharu Ueda; Ryoko Santo; Akio Ichimura
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 387 KB
- Volume
- 16
- Category
- Article
- ISSN
- 1040-0397
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✦ Synopsis
Abstract
For [PMo~12~O~40~]^3−^, the presence of Li^+^ produced a two‐electron wave at nearly the same potential as the first one‐electron wave in acetonitrile or acetone. The voltammetric behavior of [PMo~12~O~40~]^3−^ in a binary mixture of acetonitrile and solvent S was compared with those in a mixture of acetone and S. When the donor number (DN) of S>20, the first two‐electron wave was converted into one‐electron waves in such binary mixtures. The conversion occurred at lower mole fractions of S in an acetonitrile+S mixture than in an acetone+S mixture. The ^7^Li NMR results showed that the preferential solvating ability of Li^+^ with S was greater in the former mixture. A linear relationship was found between the iso‐solvation point x~iso~(S) and the reciprocal of the difference between the DNs of S and acetonitrile, which gave the basis to explain the anomalies observed for a mixture of acetonitrile and H~2~O.