The asymmetric transfer hydrogenation (ATH) of ketones/imines with Noyori Ikariya catalyst represents an important reaction in both academia and fine chemical industry. The method allows for the preparation of chiral secondary alcohols/amines with very good to excellent optical purities. Remarkably, the same chiral Noyori Ikariya complex is also a precatalyst for a wide range of other chemo- and stereoselective reductive and oxidative transformations. Among them are enantioselective sulfonamidation of acrylates (intramolecular aza-Michael reaction) and carboxylation of indoles with CO2. Development of these catalytic reactions has been inspired by the realized cleavage of the N-H bond of sulfonamides and indoles by the 16e(-) amido derivative of the 18e(-) precatalyst via metal ligand cooperation (MLC). This paper summarizes our efforts to investigate N-H bond cleavage of gaseous ammonia in solution via MLC and reports the serendipitous discovery of a new class of chiral tridentate kappa(3)[N,N',N ''] Ru and Ir metallacycles, derivatives of the famous M-FsDPEN catalysts (M = Ru, Ir). The protonation of these metallacycles by strong acids containing weakly coordinating (chiral) anions generates ionic complexes, which were identified as conceptually novel Noyori-Ikariya precatalysts. For example, the ATH of aromatic ketones with some of these complexes proceeds with up to 99% ee.