单个电子传递到易斯对:通过小分子激活向阳离子的途径
Liu Leo Liu1, Levy L Cao1, Yue Shao1
1Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
Journal of the American Chemical Society
|June 28, 2017
概括
易斯酸与十甲基铁 (Cp*2Fe) 结合,可以促进各种小分子的单电子转移反应. 这项研究探讨了新的反应途径和产物,扩大了对电子转移机制的理解.
科学领域:
- 有机金属化学
- 反应机制
- 易斯酸化学
背景情况:
- 单个电子转移 (SET) 反应是化学的基础.
- 易斯酸如E ((C6F5) 3 (E = B, Al) 是已知的激活剂.
- 十甲基铁 (Cp*2Fe) 是一个成熟的电子供体.
研究的目的:
- 在甲基烯的存在下研究易斯酸与小分子的反应性.
- 阐明单个电子转移反应的机制.
- 描述新的反应产物.
主要方法:
- 易斯酸 (B(C6F5) 3,Al(C6F5) 3) 与各种基质 (二硫化物,过氧化物,化物,O2,Se,Te,S8) 和十甲基铁) 的反应.
- 反应产物的光谱表征.
- 机理学研究包括激进路径调查.
主要成果:
- 形成独特的离子物种,包括十甲基铁和易斯酸添加物.
- 与过氧化物,二硫化物和元素石化物反应产物的鉴定.
- 证据表明与Ph3SnH和p-反应中的中间激素.
- 用TEMPO,O2,Se,Te和S8合成新的复合物.
结论:
- 易斯酸和十甲基铁的组合为SET反应提供了多功能系统.
- 根据基质观察到不同的反应途径和产物形成.
- 这项研究提供了有关这些电子转移过程的机制的见解.
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