We have prepared a series of new rhenium complexes containing chiral ferrocenyldiphosphane ligands of the Josiphos family, starting from commercially available rhenium sources. These new Re V oxido and nitrido complexes, several of which have been characterized by X-ray crystallography, are air-and moisture-stable and are active catalysts in the [a] 5021 asymmetric transfer hydrogenation of ketones using 2-propanol as the hydrogen source in the presence of substoichiometric amounts of triethylamine (TEA). The reaction proceeds cleanly with good to excellent yields (50-99 %) but with moderate enantioselectivity (up to 58 % ee). A mechanism not involving hydridic species is proposed. ketones and imines [14] and that of Kwong on the asymmetric cyclopropanation of alkenes [15] using chiral Re V and Re I catalysts stand alone. Other important achievements in the Re-catalyzed reduction of carbonyl groups have been reported by Abu-Omar [16] and Royo. [17] An important class of ligands used in those kinds of transformations are bi-, tri-or tetradentate ferrocenylphosphanes, [6b,18] which were moderately successful until Baratta and coworkers reported outstanding results [(enantioselectivity and turnover numbers (TONs)] [9,19] by using Josiphos ligands (Figure 1), some of the most successful in asymmetric catalysis and hence one of the so called "privileged ligands". [20] They have been widely used in several applications both in academia and in industry. [20b] Scheme 2. General procedure for the synthesis of Re oxido complexes.www.eurjic.org