Understanding the role of frustrated Lewis pairs as ligands in transition metal-catalyzed reactions

Abstract

The role of frustrated Lewis pairs (FLPs) as ligands in gold(I) catalyzed-reactions has been computationally investigated by using state-of-the-art density functional theory calculations. To this end, the nature of (P,B)-FLP–transition metal interactions in different gold(I)-complexes has been first explored in detail with the help of the energy decomposition analysis method, which allowed us to accurately quantify the so far poorly understood Au⋯B interactions present in these species. The impact of such interactions on the catalytic activity of gold(I)-complexes has been then evaluated by performing the Au(I)-catalyzed hydroarylation reaction of phenylacetylene with mesitylene. With the help of the activation strain model of reactivity, the factors governing the higher activity of Au(I)-complexes having a FLP as a ligand as compared to that of the parent PPh₃ system have also been quantitatively identified.