一个单质结合的催化剂失活 ((0) 复杂的结合))
Samuel H Newman-Stonebraker1,2, T Judah Raab2, Abigail G Doyle2
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
(0) 催化剂可以在催化循环后通过二分化去活化. 用基质或连接物拦截活性的物种,可以防止这种不可逆转的催化剂失活.
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.
- 合成化学 合成化学
背景情况:
- 交叉合催化剂在合成化学中是必不可少的,但有副作用.
- 了解催化剂失活路径对于优化反应和设计新的催化剂至关重要.
研究的目的:
- 为了研究与CyJohnPhos配体的单合(0) 复合物的离循环反应性.
- 阐明导致催化剂失活的二分化和CP键激活途径.
主要方法:
- () / () 和 () / (II) 二次体的结构特征.
- 在没有基质和添加剂的情况下研究的复杂反应性.
主要成果:
- 一个单质的CyJohnPhos结合的Ni(0) 复合体在减少性消除后经历二分化.
- 素联体的C-P键激活形成了一个化物桥接的Ni(0) /Ni(II) 模.
- 单体Ni(0) 物种必须被基质或连接物拦截,以防止失活.
结论:
- 对这种催化剂来说,二分化和CP键激活代表了重要的循环外失活路径.
- 连接体和基质的协调对于维持活跃的单体Ni0物种至关重要.
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