从阿佐皮里丁二甲基复合物中诱导乙的降解
Andrey E Rudenko1, Naomi E Clayman1, Katherine L Walker1
1Department of Chemistry , Stanford University , Stanford , California 94305-5080 , United States.
Journal of the American Chemical Society
|August 31, 2018
概括
在溶液中自发地从 (II) 复合物中排出乙. 氧化活性亚松连体促进了这一过程,使乙在室温下释放出来.
科学领域:
- 有机金属化学
- 催化剂
- 协调化学
背景情况:
- 减少排放 (RE) 是催化循环的一个关键步骤.
- 从Pd(II) 的基组的RE通常是缓慢的,需要激活.
- 二甲基复合物与二胺联体通常对RE稳定.
研究的目的:
- 调查Pd (II) 复合物中的自发还原性乙清除.
- 阐明氧化还原活性阿佐皮里丁配体在促进 RE 的作用.
- 了解从 (azpy) PdMe2复合物中形成乙的机制.
主要方法:
- (azpy) PdMe2复合物的合成和表征.
- 关于乙释放的依赖溶剂的研究.
- 温度控制的实验.
- 实验机械研究.
- 计算研究 (DFT).
主要成果:
- 在溶解时观察到来自 (azpy) PdMe2复合物的自发减少性乙排泄.
- 在没有外部刺激的情况下,在低温 (10°C至室温) 发生乙释放.
- 氧化活性阿佐皮里丁配体对于促进RE至关重要.
- 一个双分子甲基转移机制先于RE步骤,两者都由配体促进.
结论:
- 亚索皮里丁连接物能够从Pd中自发减少乙.
- 在甲基转移和RE中,亚索皮里丁配体的氧化还原活性起着至关重要的作用.
- 这一发现为控制催化过程中的可再生能源提供了新的途径.
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