The precise editing of surface sites on a molecular-like gold catalyst for modulating regioselectivity.

ABSTRACT: It is extremely difficult to precisely edit a surface site on a typical nanoparticle catalyst without changing other parts of the catalyst. This precludes a full understanding of which site primarily determines the catalytic properties. Here, we couple experimental data collection with theoretical analysis to correlate rich structural information relating to atomically precise gold clusters with the catalytic performance for the click reaction of phenylacetylene and benzyl azide. We also identify a specific surface site that is capable of achieving high regioselectivity. We further conduct site-specific editing on a thiolate-protected gold cluster by peeling off two monomeric RS-Au-SR motifs and replacing them with two Ph₂P-CH₂-PPh₂ staples. We demonstrate that the surface Au-Ph₂P-CH₂-PPh₂-Au motifs enable extraordinary regioselectivity for the click reaction of alkyne and azide. The editing strategy for the surface motifs allows us to exploit previously inaccessible individual active sites and elucidate which site can explicitly govern the reaction outcome.

SUBMITTER: Li S 

PROVIDER: S-EPMC8163066 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature