在硫酸上使用电友性有机 (III) 合体,用于碳化合物激活和功能化
Zoha H Syed1, David M Kaphan1, Frédéric A Perras2
1Chemical Sciences and Engineering Division , Argonne National Laboratory , Lemont , Illinois 60439 , United States.
Journal of the American Chemical Society
|March 23, 2019
概括
一种在硫酸上支持的新型催化剂在C-H键功能化和烯酸化方面表现出高活性. 这种单位催化剂结合了同质和异质的好处,提高了反应性.
科学领域:
- 有机金属化学
- 不同质的催化
- 表面科学
背景情况:
- 单位支持的催化剂结合了同质和异质的催化优势.
- 研究金属支相互作用对于催化剂设计至关重要.
- 用于碳化合物功能化的先前工作 (dmPhebox)
研究的目的:
- 在硫酸上合成和表征一个单位支持的 (dmPhebox) Ir (III) 催化剂.
- 在C-H键功能化和化反应中评估支持复合物的催化活性.
- 了解硫酸支在调节催化剂性能中的作用.
主要方法:
- 在硫酸上化学吸收 (dmPhebox) Ir (III) 复合物.
- 使用扩散反射红外里叶变换光谱 (DRIFTS),DNP增强固态NMR (SSNMR) 和X射线吸收光谱 (XAS) 的表征.
- 对脱和化的催化试验
- 密度函数理论 (DFT) 计算以调查反应机制.
主要成果:
- 在硫化上成功移植 (dmPhebox) ,使中心具有离子性质.
- 观察到高催化活性的电友C-H键功能化,包括脱.
- 通过支持的催化剂促进催化油.
- DFT计算显示β-H清除的激活障碍较低.
- 在类似条件下,支持的同类复合物没有表现出任何活性.
结论:
- 硫酸是创建高活性单位催化剂的有效支持.
- 支持的中心的阳离子性增强了C-H功能化的反应性.
- 硫酸支的独特特性对观察到的催化性能至关重要.
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