An Atomically Precise Pyrazolate‐Protected Copper Nanocluster Exhibiting Exceptional Stability and Catalytic Activity

The synthesis of atomically precise copper nanoclusters (Cu‐NCs) with high chemical stability is a prerequisite for practical applications, yet still remains a long‐standing challenge. Herein, we have prepared a pyrazolate‐protected Cu‐NC (Cu8), which exhibited exceptional chemical stability either...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-02, Vol.62 (9), p.e202218369-n/a
Main Authors: Wang, Yu‐Mei, Lin, Xiao‐Chun, Mo, Kai‐Ming, Xie, Mo, Huang, Yong‐Liang, Ning, Guo‐Hong, Li, Dan
Format: Article
Language:English
Subjects:
Catalysis
Catalytic activity
Chemical synthesis
Copper
Copper Nanocluster
Corrosion resistance
Crystals
Hydrogen peroxide
Indolizines
Ligand Transformation
Nanoclusters
NMR
Nuclear magnetic resonance
Organic acids
Pyrazolate
Single crystals
Stability
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Summary:The synthesis of atomically precise copper nanoclusters (Cu‐NCs) with high chemical stability is a prerequisite for practical applications, yet still remains a long‐standing challenge. Herein, we have prepared a pyrazolate‐protected Cu‐NC (Cu8), which exhibited exceptional chemical stability either in solid‐state or in solution. The crystals of Cu8 are still suitable for single crystal X‐ray diffraction analysis even after being treated with boiling water, 8 wt % H2O2, high concentrated acid (1 M HCl) or saturated base (≈20 M KOH), respectively. More importantly, the structure of Cu8 in solution also remained intact toward oxygen, organic acid (100 eq. HOAc) or base (400 eq. dibutylamine) confirmed by 1H NMR and UV/Vis analysis. Taking advantage of high alkali‐resistant, Cu8 illustrates excellent catalytic activity for the synthesis of indolizines, and it can be reused for at least 10 cycles without losing catalytic performance. An atomically precise pyrazolate‐protected copper nanocluster exhibits extraordinary chemical stability toward oxygen, heat, oxidant (8 wt % H2O2), acid (1 M HCl) and base (20 M KOH). It has been used as stable homogeneous catalysts for synthesis of indolizine with exceptional catalytic activity, delivering superior TOF (3380 h−1) compared to other reported catalysts.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202218369