Jia Teng, Ai Jie, Li Xiaoguang, Zhang Miao-Miao, Hua Yue, Li Yi-Xin, Sun Cai-Fang, Liu Feng, Huang Ren-Wu, Wang Zheng, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Institute for Advanced Study, Shenzhen University, Shenzhen, 518060, China.
Nat Commun. 2024 Nov 5;15(1):9551. doi: 10.1038/s41467-024-53950-7.
The hydroboration of alkynes into vinylboronate esters is a vital transformation, but achieving high chemoselectivity of targeted functional groups and an appreciable turnover number is a considerable challenge. Herein, we develop two dynamically regulating dual-catalytic-site copper clusters (CuNC and CuNC) bearing N-heterocyclic thione ligands that endow CuNC and CuNC catalysts with performance. In particular, the performance of microcrystalline CuNC in hydroboration is characterized by a high turnover number (77786), a high chemoselectivity, high recovery and reusability under mild conditions. Mechanistic studies and density functional theory calculations reveal that, compared with the CuNC catalyst, the CuNC catalyst has a lower activation energy for hydroboration, accounting for its high catalytic activity. This work reveals that precisely constructed cluster catalysts with dual catalytic sites may provide a way to substantially improve catalytic properties by fully leveraging synergistic interactions and dynamic ligand effects, thus promoting the development of cluster catalysts.
将炔烃硼氢化生成乙烯基硼酸酯是一个重要的转化过程，但要实现目标官能团的高化学选择性和可观的周转数是一项相当大的挑战。在此，我们开发了两种带有N-杂环硫酮配体的动态调节双催化位点铜簇（CuNC和CuNC），这些配体赋予了CuNC和CuNC催化剂性能。特别是，微晶CuNC在硼氢化反应中的性能表现为高周转数（77786）、高化学选择性、在温和条件下具有高回收率和可重复使用性。机理研究和密度泛函理论计算表明，与CuNC催化剂相比，CuNC催化剂在硼氢化反应中具有较低的活化能，这解释了其高催化活性。这项工作表明，精确构建的具有双催化位点的簇催化剂可能通过充分利用协同相互作用和动态配体效应提供一种大幅提高催化性能的方法，从而推动簇催化剂的发展。
