氧化添加,电子转移或原子抽象
Justin B Diccianni1, Joseph Katigbak1, Chunhua Hu1
1Department of Chemistry , New York University , 100 Washington Square East , New York , New York 10003 , United States.
Journal of the American Chemical Society
|January 8, 2019
概括
这项研究实验显示, (I) 复合物通过协同的原子抽象激活化物,形成基. 这一发现阐明了催化交叉合反应的关键步骤.
科学领域:
- 有机金属化学
- 催化剂
- 反应机制
背景情况:
- 在Ni-催化交叉合中,单电子氧化激活基化物至关重要.
- 提出的四种机制包括氧化添加,外层电子转移,内层电子转移和协同原子抽象.
- 之前的研究依赖于计算数据,缺乏对Ni (I) 中介基形成途径的实验验证.
研究的目的:
- 通过实验研究和区分化介导激活的机制.
- 为了分离和描述 (Xantphos) Ni (I) -Ar复合物,进行动力学研究.
- 在Ni催化交叉合反应中阐明激素生成的特定途径.
主要方法:
- 对 (Xantphos) Ni (I) -Ar复合物的分离和表征.
- 检查固体,电子和溶剂效应的动力学研究.
- 用密度函数理论 (DFT) 计算来评估反应路径.
主要成果:
- 分离的 () -Ar复合物选择性地激活基化物而不是基化物.
- 动力和计算数据证实了化激活的协同原子抽象机制.
- 这与在相关的烯化物激活中观察到的外球电子转移机制形成鲜明对比.
结论:
- 中介化激活是通过协同的原子抽象进行的.
- 这种机理性洞察力澄清了Ni催化交叉合中的基质形成.
- 在交叉电友合反应中提供电友分化的基础.
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