Deciphering the Primary Role of Au···H‐X Hydrogen Bonding in Gold Catalysis

Au···H‐X (X = N or C) hydrogen bonding is gaining increasing interest, both in the study of its intrinsic nature and in their operability in different fields. While the role of these interactions has been studied in the stabilization of gold(I) complexes, their role during the minimum free energy reaction pathway of a given catalytic process remains unexplored. We report herein that complex [Au(CºCPh)(pip)] (pip = piperidine) catalyses the A3‐coupling reaction for the synthesis of propargylamines, thanks to the ability of Au(I) to promote weak hydrogen bonding interactions with the reactants along the free energy profile. Density Functional Theory (DFT) calculations show that these Au···H‐X interactions play a directing role in the catalysed A3‐coupling. Topological non‐covalent interactions (NCI), interaction region indicator (IRI) and quantum theory of atoms in molecules (QTAIM) analysis in real space of the electron density provides a description of these interactions accurately.