AI Article Synopsis
- - The study focuses on using carboranyls (CBs) as new functional ligands for stabilizing gold nanoparticles (AuNPs), addressing challenges in nanocatalysis like metal leaching and structural changes.
- - The synthesized CB@AuNPs demonstrate remarkable stability under various conditions and outperform traditional AuNP catalysts by preventing the dissolution of active gold species during reactions.
- - The research reveals that CB@AuNPs achieve high selectivity in aromatic bromination of different arenes, highlighting the importance of carboranyl ligands for achieving regioselective transformations.
Article Abstract
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 (E=-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(Au)-satellite(CBAu) structure, showing high stability towards multiple stimuli (110 °C, pH=1-12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh) 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.
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| http://dx.doi.org/10.1002/anie.202409283 | DOI Listing |
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