Mechanistic insights into carbon–carbon coupling on NiAu and PdAu single-atom alloys

Carbon–carbon coupling is an important step in many catalytic reactions, and performing sp3–sp3 carbon–carbon heterogeneously particularly challenging. It has been reported that PdAu single-atom alloy (SAA) model surfaces are able to selectively couple methyl groups, producing ethane from iodide. Herein, we extend this study NiAu SAAs find Ni atoms Au active for C–I cleavage selective produce ethane. Furthermore, perform ab initio kinetic Monte Carlo simulations include the effect of iodine atom, which was previously considered a bystander species. We exhibit similar chemistry PdAu, but reason similarity due role play terms blocking atom sites. Specifically, on SAAs, outcompete groups occupancy sites leaving Me Au, while binding strengths at Pd site more similar. These shed light mechanism SAAs. discuss reaction energetics make analogy between as blocker heterogeneous catalyst homogeneous catalysts ligands must detach order be accessed by reactants.