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

Author:

Wang Mengyue12,Zhang Shengye32,Gong Yue42,Zhang Wangyang12,Wang Yu5,Chen Yupeng12,Zheng Qiang42,Liu Zhipan36,Tang Cen12ORCID

Affiliation:

1. CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety National Center for Nanoscience and Technology Beijing 100190 China

2. University of Chinese Academy of Sciences Beijing 100049 China

3. The State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, CAS Shanghai 200032 China

4. CAS Key Laboratory of Standardization and Measurement for Nanotechnology National Center for Nanoscience and Technology Beijing 100190 China

5. Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory Shanghai Advanced Research Institute, CAS Shanghai 201204 China

6. Department of Chemistry Fudan University Shanghai 200433 China

Abstract

AbstractAchieving 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.

Funder

Youth Innovation Promotion Association of the Chinese Academy of Sciences

Publisher

Wiley

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