This is a personal account of the application of ruthenium complexes containing chiral tetradentate ligands with a P₂N₂ ligand set (PNNP) as catalyst precursors for enantioselective “atom transfer” reactions. Therewith are meant reactions that involve bond formation between a metal-coordinated molecule and a free reagent. The reactive fragment (e.g. carbene) is transferred either from the metal to the non-coordinated substrate (e.g. olefin) or from the free reagent (e.g. F⁺) to the metal-bound substrate (e.g. β-ketoester), depending on the class of catalyst (monocationic, Class A; or dicationic, Class B). The monocationic five-coordinate species [RuCl(PNNP)]⁺ and the six-coordinate complexes [RuCl(L)(PNNP)]⁺ (L = Et₂O, H₂O) of Class A catalyse asymmetric epoxidation, cyclopropanation (carbene transfer from the metal to the free olefin), and imine aziridination. Alternatively, the dicationic complexes [Ru(L–L)(PNNP)]²⁺ (Class B), which contain substrates that act as neutral bidentate ligands L–L (e.g., β-ketoesters), catalyse Michael addition, electrophilic fluorination, and hydroxylation reactions. Additionally, unsaturated β-ketoesters form dicationic complexes of Class B that catalyse Diels–Alder reactions with acyclic dienes to produce tetrahydro-1-indanones and estrone derivatives. Excellent enantioselectivity has been achieved in several of the catalytic reactions mentioned above. The study of key reaction intermediates (both in the solid state and in solution) has revealed significant mechanistic aspects of the catalytic reactions.