Jia Teng, Li Yi-Xin, Ma Xiao-Hong, Zhang Miao-Miao, Dong Xi-Yan, Ai Jie, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostcal Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, P. R. China.
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, P. R. China.
Nat Commun. 2023 Oct 28;14(1):6877. doi: 10.1038/s41467-023-42688-3.
Three-component dehydrogenative coupling reactions represent important and practical methodologies for forging new C-N bonds and C-C bonds. Achieving highly all-in-one dehydrogenative coupling functionalization by a single catalytic system remains a great challenge. Herein, we develop a rigid-flexible-coupled copper cluster [Cu(NHC)(PF)] (CuNC) using a tridentate N-heterocyclic carbene ligand. The shell ligand endows CuNC with dual attributes, including rigidity and flexibility, to improve activity and stability. The CuNC is applied to catalyze both highly all-in-one dehydrogenative coupling transformations. Mechanistic studies and density functional theory illustrate that the improved regioselectivity is derived from the low energy of ion pair with copper acetylide and endo-iminium ions and the low transition state, which originates from the unique physicochemical properties of the CuNC catalyst. This work highlights the importance of N-heterocyclic carbene in the modification of copper clusters, providing a new design rule to protect cluster catalytic centers and enhance catalysis.
三组分脱氢偶联反应是形成新的碳氮键和碳碳键的重要实用方法。通过单一催化体系实现高度一体化的脱氢偶联官能化仍然是一个巨大的挑战。在此，我们使用三齿氮杂环卡宾配体开发了一种刚柔耦合的铜簇[Cu(NHC)(PF)]（CuNC）。壳层配体赋予CuNC刚性和柔韧性双重属性，以提高活性和稳定性。CuNC被应用于催化两种高度一体化的脱氢偶联转化反应。机理研究和密度泛函理论表明，提高的区域选择性源于与乙炔铜和内亚胺离子形成的离子对能量较低以及过渡态能量较低，这源于CuNC催化剂独特的物理化学性质。这项工作突出了氮杂环卡宾在修饰铜簇中的重要性，为保护簇催化中心和增强催化作用提供了新的设计规则。
