Highly Stable Carboranyl Ligated Gold Nano‐Catalysts for Regioselective Aromatic Bromination

Achieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal‐ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carborany...

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Published in:Angewandte Chemie 2024-09, Vol.136 (39), p.n/a
Main Authors: Wang, Mengyue, Zhang, Shengye, Gong, Yue, Zhang, Wangyang, Wang, Yu, Chen, Yupeng, Zheng, Qiang, Liu, Zhipan, Tang, Cen
Format: Article
Language:English
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Summary:Achieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal‐ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carboranyls (CBs) as unprecedented carbon‐bonded functional ligands (Eads.CB‐Au(111)=−2.90 eV) for gold nanoparticles (AuNPs), showcasing their exceptional stabilization capability that is attributed by strong Au−C bonds combined with B−H⋅⋅⋅Au interactions. The synthesized CB@AuNPs exhibit core(Aun)‐satellite(CB2Au−) structure, showing high stability towards multiple stimuli (110 °C, pH=1–12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh3) stabilized AuNPs, dissolution of catalytically active gold species was suppressed in CB@AuNPs under the reaction conditions. Leveraging these distinct features, CB@AuNPs realized outstanding p : o selectivities in aromatic bromination. Unbiased arenes including chlorobenzene (up to >30 : 1), bromobenzene (15 : 1) and phenyl acrylate were examined using CB@AuNPs as catalysts to afford highly‐selective p‐products. Both carboranyl ligands and carboranyl derived counterions are crucial for such regioselective transformation. This work has provided valuable insights for AuNPs in realizing diverse regioselective transformations. Carboranes are disclosed to generate highly stable CB@AuNPs of core‐satellite structures. They are capable of suppressing active species dissolution under harsh conditions and have realized regioselective bromination of unbiased arenes with p : o selectivities comparable if not superior to those in the best selective non‐enzyme catalytic systems.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202409283