Flash-Quench Technique Employed To Study the One-Electron Reduction of Triiodide in Acetonitrile: Evidence for a Diiodide Reaction Product
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- 作者：Byron H. Farnum ; James M. Gardner ; Gerald J. Meyer
- 刊名：Inorganic Chemistry
- 出版年：2010
- 出版时间：November 15, 2010
- 年：2010
- 卷：49
- 期：22
- 页码：10223-10225
- 全文大小：730K
- 年卷期：v.49,no.22(November 15, 2010)
- ISSN：1520-510X
文摘
The one-electron reduction of triiodide (I3−) by a reduced ruthenium polypyridyl compound was studied in an acetonitrile solution with the flash-quench technique. Reductive quenching of the metal-to-ligand charge-transfer excited state of [RuII(deeb)3]2+ by iodide generated the reduced ruthenium compound [RuII(deeb−)(deeb)2]+ and diiodide (I2•−). The subsequent reaction of [RuII(deeb−)(deeb)2]+ with I3− indicated that I2•− was a product that appeared with a second-order rate constant of (5.1 ± 0.2) × 109 M−1 s−1. After correction for diffusion and some assumptions, Marcus theory predicted a formal potential of −0.58 V (vs SCE) for the one-electron reduction of I3−. The relevance of this reaction to solar energy conversion is discussed.