从联中减少的消除 (II) 胺基复合物形成 sp3 碳键
D Matthew Peacock1, Quan Jiang2, Patrick S Hanley1
1Department of Chemistry , University of California , Berkeley , California 94720 , United States.
Journal of the American Chemical Society
|March 15, 2018
概括
研究人员探索了与相关联的基 () 胺复合物,发现基物质对形成基键的减少率有显著影响. 固体阻碍或电子贫乏的配体减缓了反应.
科学领域:
- 有机金属化学
- 催化剂
- 反应机制
背景情况:
- 在有机合成中,催化交叉合反应至关重要.
- 对于设计高效的催化系统来说,了解减排是关键.
- 通过从复合物中减少消除键的形成是一个重要的转化.
研究的目的:
- 为了研究基二复合物的形成.
- 确定控制减排反应速率的因素.
- 为了比较不同的配体系统在减少性消除中的反应性.
主要方法:
- 合成与相关联的基 (II) 胺复合物.
- 测量反应速率的实验动力学研究.
- 计算 (DFT) 研究以阐明反应途径和能量障碍.
- 化物和素配体的电子和硬质性质不同.
主要成果:
- 与NHC结合的复合物相比,从t-Bu3P结合的复合物中减少的消除显示出较低的自由能量障碍.
- 较少的电子丰富或更硬质阻碍的基体的反应速率下降.
- 具有P,O配体的四坐标复合体比三坐标复合体具有较慢的还原性消除.
- 在P,O配体中,灵活的连接剂通过使配体解离,促进了更快的还原性消除.
结论:
- 连接体电子和固体极大地影响了还原性淘汰的速度.
- 三坐标的复合物通常比四坐标的更具反应性.
- 灵活的P,O配体可以通过涉及Pd-O键延长或解离的协调机制来提高减少性消除率.
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