Ag13Cu4 Nanocluster-Catalyzed Ambient C-F Bond Activation
Year: 2026
Type: preprint
Abstract: Atomically precise nanoclusters (NC) with discrete electronic states and high surface-to-atom ratios offer unique controllable active sites leading to unique catalytic transformations. Here we demonstrate that an ultrasmall (<3 nm), atomically precise Ag-Cu alloy NC, [Ag13Cu4(o1-CBT)12]3- (o1-CBT = ortho-1-carboranethiol) (Ag13Cu4), leverages these features to accomplish the extremely difficult activation and cleavage of inert C-F bond under ambient conditions. With copper atoms positioned at peripheral sites, Ag13Cu4 catalyzes room-temperature C-N cross-coupling between aryl fluorides and the pharmacologically relevant thioguanine (TG) under aerobic conditions, delivering arylated TG derivatives under operationally simple conditions. Computations revealed the evolution of atomic arrangements, superatom-delocalized electronic states of the bimetallic NC, frontier orbitals of gap-localized Cu and reactants, activation mechanism and a barrier-crossing pathway of the catalyzed reaction, culminating with the uncovering of a concerted SNAr mechanism of the reaction enabling C-F bond-activation and cleavage of benzene fluoride with a cross-coupling transformation forming a C-N bond between the phenyl group and TG molecule. This first demonstration of ambient C-F bond dissociation by an atomically precise cluster highlights a molecular materials-driven frontier in catalysis, opening futuristic pathways for synthesizing fluorinated pharmaceuticals and remediation of fluorinated environmental contaminants.
Source: ChemRxiv
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7207568174