Reactivity and Mechanism of Recoverable Pd₁@C₃N₄ Single-Atom Catalyst in Buchwald–Hartwig Aminations

Buchwald–Hartwig (BH) aminations are crucial for synthesizing arylamine motifs in numerous bioactive molecules and fine chemicals. While homogeneous palladium complexes can be effective catalysts, their high costs and environmental impact motivate the search for alternative approaches. Heterogeneous palladium single-atom catalysts (SAC) offer promising recoverable alternatives in C–C cross-couplings. Yet their use in C–N couplings remains unexplored, and mechanistic insights into amine coupling with aryl halides over solid surfaces that could guide catalyst design are lacking. Here, we demonstrate that palladium atoms coordinated to well-defined heptazinic cavities of graphitic carbon nitride (Pd1@C3N4) deliver practically relevant yields for BH couplings across various aryl halides and amines, exhibiting persistent activity and negligible leaching over several cycles. Notably, Pd1@C3N4 shows comparable or superior activity with certain aryl chlorides to bromides, alongside high chemoselectivity for amines over amides. In situ X-ray absorption spectroscopy analyses supported by density functional theory simulations identify the concerted role of the ligand and the C3N4 host in determining the performance, with a Pd(II) nominal oxidation state observed under all coupling conditions. Complementary structural and kinetic studies highlight a distinct reaction mechanism than that typically reported for homogeneous catalysts. These findings offer key insights for designing recyclable SAC for BH coupling, setting the basis for extending the scope toward more complex industrial targets.