How Do Secondary Phosphine Oxides Interact with Silver Nanoclusters? Insights from Computation

Air-stable nanoparticles stabilized with secondary phosphine oxides (SPOs) can have a remarkable role as catalysts. Since size and activity depend both on the cluster-ligand interaction and the nature of the employed ligand, the present work provides a fresh perspective on the prospects of bonding analysis, rationalizing for the first time the physical nature of interactions between silver nanoclusters (SNCs) and secondary phosphine oxides (SPOs) in the light of energy decomposition (EDA-NOCV) and noncovalent interaction (NCI) analyses, using the silver core of the X-ray structure for a highly symmetric, ligand-decorated Ag44 cluster available in the literature. Our findings reveal that phosphines containing aliphatic substituents are more stabilized when interacting with Ag cluster, in contrast to aromatic groups, and that SPOs containing aromatic moieties become aligned to the silver surface upon adsorption. This alignment of aromatic substituents substantially contribute to dispersion interactions, whi...