钯催化剂上还原胺化反应的基础机理：羟基在生成位阻胺中独特的作用。
Underlying Mechanisms of Reductive Amination on Pd-Catalysts: The Unique Role of Hydroxyl Group in Generating Sterically Hindered Amine.
机构信息
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
Institute of Zhejiang University-Quzhou, 78 Jiuhua Boulevard North, Quzhou 324000, China.
出版信息
Int J Mol Sci. 2022 Jul 10;23(14):7621. doi: 10.3390/ijms23147621.
Pd nanospecies supported on porous g-C3N4 nanosheets were prepared for efficient reductive amination reactions. The structures of the catalysts were characterized via FTIR, XRD, XPS, SEM, TEM, and TG analysis, and the mechanisms were investigated using in situ ATR−FTIR spectroscopic analysis complemented by theoretical calculation. It transpired that the valence state of the Pd is not the dominating factor; rather, the hydroxyl group of the Pd(OH)2 cluster is crucial. Thus, by passing protons between different molecules, the hydroxyl group facilitates both the generation of the imine intermediate and the reduction of the C=N unit. As a result, the sterically hindered amines can be obtained at high selectivity (>90%) at room temperature.
负载在多孔 g-C3N4 纳米片上的 Pd 纳米物种被用于高效的还原胺化反应。通过 FTIR、XRD、XPS、SEM、TEM 和 TG 分析对催化剂的结构进行了表征，并通过原位 ATR-FTIR 光谱分析结合理论计算研究了其反应机制。结果表明，Pd 的价态不是主导因素，而是 Pd(OH)2 簇中的羟基基团起着关键作用。因此，通过不同分子之间的质子传递，羟基基团促进了亚胺中间体的生成和 C=N 单元的还原。因此，在室温下可以高选择性（>90%）获得空间位阻胺。
Zotero 插件