如何控制PdII-Phenyl和CuI-Alkyl复合体之间的倒置与保留转金属化:理论见解
Hong Zheng1, Kazuhiko Semba2, Yoshiaki Nakao2
1Fukui Institute for Fundamental Chemistry, Kyoto University , Takano-Nishi-hiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan.
Journal of the American Chemical Society
|September 20, 2017
概括
在Pd/Cu催化中,转金属化的立体化学是由CaHMeR组的电子特性控制的. 结合稳定了反转,而基和乙烯基组则有利于保留机制.
科学领域:
- 有机金属化学
- 催化剂
- 计算化学
背景情况:
- 转金属化是/铜合作催化交联反应的一个关键步骤.
- 对于设计高效的催化系统来说,了解转移的立体化学结果至关重要.
研究的目的:
- 研究Pd (Br) (Ph) (A) (PCyp) (sub) (sub) 和Cu (C) (HMePh) (B) (NHC) 之间的传递机制.
- 在传递过程中阐明控制Ca原子立体化学的因素 (反转与保留).
主要方法:
- 用密度功能理论 (DFT) 的计算来研究转移途径.
- 过渡状态结构的分析,包括几何和轨道相互作用.
- 对不同传播途径的激活的评估 (ΔS°‡).
主要成果:
- 转金属化CaHMePhB的过程是立体化学的反转,通过化和Ca2p轨道进行稳定.
- CaHMeEt和CaHMe(CHCH2的转金属化发生在保留中,这是由于逆转途径中缺乏有效的结合.
- 在环上提取电子的替代物有利于反转,而固态因素和配体特性也会影响立体化学结果.
结论:
- 转移的立体化学结果是由CaHMeR组的电子性质及其稳定过渡状态的能力决定的.
- 通过修改替代剂和配体来调整催化系统,以控制转移阶段的立体化学.
- 这项研究提供了对合作Pd/Cu催化机制的基本见解.
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