电子转移反应:KO tBu (但不是NaO tBu) 在可见光激活下减少
Giuseppe Nocera1, Allan Young1, Fabrizio Palumbo1
1Department of Pure and Applied Chemistry , University of Strathclyde , 295 Cathedral Street , Glasgow , G1 1XL , U.K.
Journal of the American Chemical Society
|July 12, 2018
概括
从三氧化到的电子转移是光激活的,而不是直接的. 一种与结合的复合物,在暴露于光线时能够转移电子,并观察到金属的选择性.
科学领域:
- 摄影化学
- 有机化学
- 物理化学
背景情况:
- 关于三氧化 (KOtBu) 和烯之间的电子转移存在争议.
- 热力学潜力表明直接的电子转移不太可能.
研究的目的:
- 解决围绕KOtBu-烯电子转移的争议.
- 研究电子转移的机制和条件.
- 在这个反应中探索金属离子的选择性.
主要方法:
- 包括UV-Vis光谱和反应产品分析在内的实验研究.
- 计算方法包括时间依赖密度函数理论 (TDDFT).
- 不同的金属基 (KOtBu与NaOtBu) 和反应条件 (明亮与黑暗).
主要成果:
- 在KOtBu和之间形成桥复合体,转移吸收光谱.
- 光激活 (365/400 nm或日光) 诱导电子转移,形成基基.
- 反应对KOtBu而不是NaOtBu具有选择性,并提供了机理化.
- 激素碎片和捕获,以及BHAS合,提供电子转移的化学证据.
结论:
- 从KOtBu到的电子转移是光激活的,发生在预先形成的复合体内.
- 离子在复杂的形成和反应途径中起着至关重要的作用.
- 观察到的金属选择性得到了机械解释,为离子效应提供了新的见解.
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