Planar chiral chromium- and ruthenium-based arene complexes were prepared with high levels of enantioselectivity via a Pd-catalyzed asymmetric hydrogenolysis reaction using a bulky chiral phosphoramidite ligand. Key elements for the efficiency of the process are the use of DABCO as borane-trapping reagent as well as substantial kinetic resolution, which was found to enhance the stereochemical outcome of the reaction.