Atomically Precise Metal Nanoclusters as Single Electron Transferers for Hydroborylation

• Published in: Precision Chemistry Vol. 1; no. 3; pp. 175 - 182
• Main Authors: Zhu, Wanli, Zhang, Sheng, Fan, Weigang, Yang, Ying, Zhao, Hongliang, Fei, Wenwen, Bi, Hong, He, Jian, Li, Man-Bo, Wu, Zhikun
• Format: Journal Article
• Language: English
• Published: University of Science and Technology of China and American Chemical Society 22.05.2023; American Chemical Society
• Subjects: hydroborylation; boryl radical; atomically precise metal nanocluster; single electron transfer; tandem catalysis
• ISSN: 2771-9316; 2771-9316
• DOI: 10.1021/prechem.3c00003

The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure–property correlations at the nanoscale. However, a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters. Here, we introduce a novel catalytic mode for metal nanoclusters, in which the nanoclusters initiate the catalysis via single electron transfer (SET) without destroying the integrity of nanoclusters, providing a solution for the contradiction between activity and stability of metal nanoclusters. We illustrated that the novel activation mode featured low catalyst loading (0.01 mol %), high TOF, mild reaction conditions, and easy recycling of catalyst in alkyne hydroborylation, which often suffered from poor selectivity, low functional group tolerance, etc. Furthermore, the catalyst [Au1Cu14(TBBT)12(PPh3)6]+ (TBBTH: p-tert-butylthiophenol) can be applied in highly efficient tandem processes such as hydroborylation–deuteration and hydroborylation–isomerization, demonstrating the utility of the introduced activation mode for metal nanoclusters.