The proposed method allows to efficiently determine the atomic arrangement in bimetallic nanoparticles based on electronic structure calculations and unravels the relationship between structural preferences of atoms and binding in nanoalloys.

The reaction mechanism of the gold(I)-phosphine-catalyzed hydroamination of 1,3-dienes was analyzed by means of density functional methods combined with polarizable continuum models. Several mechanistic pathways for the reaction were considered and evaluated. It was found that the most favorable series of reaction steps include the ligand substitution reaction in the catalytically active Ph3PAuOTf species between the triflate and the substrate, subsequent nucleophile attack of the N-nucleophile (benzyl carbamate) on the activated double bond, which is followed by proton transfer from the NH2 group to the unsaturated carbon atom. The latter step, the most striking one, was analyzed in detail, and a novel pathway involving tautomerization of benzyl carbamate nucleophile assisted by triflate anion acting as a proton shuttle was characterized by the lowest barrier, which is consistent with experimental findings.

Surface oxygen sites on CeO2 nanostructures are able to bind atoms of various transition metals strong enough to prevent their sintering. This finding opens a knowledge-driven way to prepare stable single-atom catalysts with maximum metal efficiency.