使用分子氧和二氧化碳的双功能金属有机层
Wenjie Shi1,2, Yangjian Quan1, Guangxu Lan1
1Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|October 1, 2021
概括
我们设计了双功能金属有机层 (MOLs) 进行双重催化, 这些MOL提供了一个可调的平台,用于集成多个催化站点.
科学领域:
- 材料科学
- 催化剂
- 超分子化学
背景情况:
- 与传统合成相比,双重催化反应提供了增强的原子和步骤经济性.
- 协同催化的一个主要限制是所需的催化剂的不兼容性.
- 金属有机层 (MOLs) 为集成多种催化功能提供了一个有希望的平台.
研究的目的:
- 设计和合成新的双功能金属有机层 (MOLs) 用于并行催化转换.
- 在这些双重反应中使用O2和CO2.
- 使用计算方法研究催化机制.
主要方法:
- 作为易斯酸性中心的三层 (OTf) 覆盖的Hf6二级建筑单元 (SBU) 的设计和合成.
- 将金属化TPY连接物作为MOL中的金属活性位点.
- 密度函数理论 (DFT) 计算以阐明反应机制.
主要成果:
- 已经成功合成了HfOTf-Fe和HfOTf-Mn双功能MOL.
- 通过双重氧化和化,HfOTf-Fe证明了碳化合物的高效转化为蓝.
- 通过二氧化和二氧化碳插入,HfOTf-Mn促进了烯转化为烯碳酸盐.
- DFT计算显示了参与 sp3 C-H 键氧化的高旋转 FeIV (S = 2) 中心.
结论:
- 双功能MOL可以有效地整合多个催化站点进行复杂的协奏转换.
- 开发的MOL在利用O2和CO2作为核心活性剂方面表现出高效率.
- 这项工作突显了MOL作为设计先进催化系统的可调平台的潜力.
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