Atomically precise copper clusters with dual sites for highly chemoselective and efficient hydroboration

Teng Jia, Jie Ai, Xiaoguang Li, Miao-Miao Zhang, Yue Hua, Yi-Xin Li, Cai-Fang Sun, Feng Liu, Ren-Wu Huang (), Zheng Wang () and Shuang-Quan Zang ()
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Teng Jia: Zhengzhou University
Jie Ai: Zhengzhou University
Xiaoguang Li: Shenzhen University
Miao-Miao Zhang: Zhengzhou University
Yue Hua: Zhengzhou University
Yi-Xin Li: Zhengzhou University
Cai-Fang Sun: Zhengzhou University
Feng Liu: LTD
Ren-Wu Huang: Zhengzhou University
Zheng Wang: Shenzhen University
Shuang-Quan Zang: Zhengzhou University

Nature Communications, 2024, vol. 15, issue 1, 1-13

Abstract: Abstract 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 (Cu4NC and Cu8NC) bearing N-heterocyclic thione ligands that endow Cu4NC and Cu8NC catalysts with performance. In particular, the performance of microcrystalline Cu4NC 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 Cu8NC catalyst, the Cu4NC 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.

Date: 2024
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DOI: 10.1038/s41467-024-53950-7

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