Fifty years of nucleophilic substitution in the gas phase

Bimolecular nucleophilic substitution ([Formula: see text]) reactions have become a model system for the investigation of structure–reactivity relationships, stereochemistry, solvent influences, and detailed atomistic dynamics. In this review, the progress during five decades of experimental and theoretical research on gas phase [Formula: see text] reactions is discussed. Many advancements of the employed methods have led to a tremendous increase in our understanding of the properties and the dynamics of these reactions. For reactions involving six atoms a quantitative agreement of the differential reactive scattering cross sections has already been achieved, in the future it is expected that even larger polyatomic reactions systems become tractable. Furthermore, studies with higher precision, improved reactant control, and a more accurate theoretical treatment of quantum effects are envisioned.