的C-H键的激活:在bis (pyridyl) (II) 复合物中的选择性和反应性
Fenbao Zhang1, Christopher W Kirby, Douglas W Hairsine
1Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
Journal of the American Chemical Society
|October 13, 2005
概括
复合物催化了的C-H键激活. 双酸连接体影响反应结果,甲基和甲基替代剂以不同的方式指导选择性.
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:
- 复合物是有机合成中的有价值的催化剂.
- 了解连接体效应对于控制C-H激活反应中的反应性和选择性至关重要.
研究的目的:
- 为了研究 bis ((pyridyl) 连接体对催化 C-H 键激活作用的影响.
- 探索替代剂对金属化物区域选择性的影响.
主要方法:
- 在三乙醇中,二甲基复合物的反应与B(C6F5) 3/H2O.
- 使用与不同替代物 (甲基,甲氧) 配合的 (Ar-H) 作为基质.
- 基于联结体化和替代物效应的产品形成分析.
主要成果:
- 烯产物[PtAr{HOB{(C6F5) 3}{LL) ]的形成取决于由bis{(pyridyl) 连接体形成的酸盐环大小 (六个成员优于五个成员).
- 甲基替代的体表现出对金属化的meta > para > ortho选择性.
- 甲基替代的基表现出一个ortho > meta,对化有选择性.
结论:
- 双酸连接体的化模式决定了催化C-H功能化的可行性.
- 在确定C-H化的区域选择性方面,基层上的替代物标识起着至关重要的作用,电子和硬质因素可能决定了观察到的偏好.
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