在Pd(0) 和Pd(II) 上,对硬质要求高的混合型伊米达酸连接体的协调变化
Douglas B Grotjahn1, Yi Gong, Lev Zakharov
1Department of Chemistry and Biochemistry, San Diego State University, California 92182-1030, USA. grotjahn@chemistry.sdsu.edu
Journal of the American Chemical Society
|January 13, 2006
概括
研究人员探索了低坐标有机金属复合体的新杂交配体,发现重的氨酸替代剂有利于化. 这项工作提供了通过连接体设计在催化中控制反应速率和产品的见解.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 连接体设计 连接体设计
背景情况:
- 低坐标的有机金属复合物对于催化是至关重要的.
- 混合配体,使得hemilability和二次相互作用正在获得关注.
- 了解控制这些联结体特性的因素是必不可少的.
研究的目的:
- 为了合成和研究新的伊米达-2-啡联体.
- 为了探索由此产生的复合物的协调行为.
- 了解连接体结构如何影响氧化加法中的反应性.
主要方法:
- 合成了三种新型的imidazol-2-ylphosphine连接体,其硬质体质量不同.
- 两个坐标的L2Pd(0) 复合体的形成和表征.
- 使用X射线衍射和NMR光谱学对氧化添加反应的研究.
主要成果:
- 合成的L2Pd(0) 复合体存在于两个坐标,12电子的物种.
- 在氧化添加剂中的反应结果可以通过配体替代剂和基质进行调整.
- 大量的氨酸组 (三-丁) 促进eta(2) -P,N化,形成单体复合物.
- 在一个离子复合体中观察到血溶性,其带交换取决于温度.
- 在imidazole周围的固体阻碍会影响 Pd-N 键的长度.
结论:
- 结体质量是控制复合物的协调和反应性的关键因素.
- 伊米达-2-ylphosphine连接物提供可调整的溶化能力和二次相互作用能力.
- 这项研究为设计先进的有机金属催化剂提供了基础.
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