The syntheses of Δ ʌ-, Δ-, and ʌ-[Ru(bpy) 2(1 1,r R-chxn)] 2+ (where 1 R,2 R-chxn=(1 R,2 R)-(−)-1,2-diaminocyclohexane); rac.-. Δ-, and ʌ-[Ru(bpy) 2(chxdiim) 2+ (where chxdiim=1,2-diiminocyclohexane); rac.-, and Δ-[Ru(bpy) 2(dmen)] 2+ (where dmen = N,N′-(dimethyl)ethylenediamine), and rac.-, and Δ-[Ru(bpy) 2(dmdiim)] 2+ (where dmdiim = N,N′-(dimethyl)ethylenediimine) are described. Oxidation of the coordinated diamines with an acid solution of Ce (IV) and reduction of the coordinated diimines with NaBD 4 occur under retention of the configuration at the metal center. Reduction of the diimine complexes with NaBD 4 gives back the amines with a diastereomeric excess (ʌ- R,R and Δ- S,S) of 60% in case of chxn as a ligand and 80% for the dmen ligand. The latter becomes a chiral ligand upon deuteration. The reduction also yields a small amount (up to 10%) of the corresponding cis isomers (Δ- R,S/ʌ- S,R). In addition, semi-reduced coordinated amine/imine ligands are observed as intermediates. The identity of the reaction products as well as their configurations has been established by means of circular dichroism and 1H NMR spectroscopy.