The ability of transition metal catalysts to add or remove hydrogen from organic substrates by transfer hydrogenation is a valuable synthetic tool. Towards a series of novel metal complexes with a P―NH ligand, [Ph2PNHCH2―C4H3O] derived from furfurylamine were synthesized. Reaction of [Ph2PNHCH2―C4H3O] 1 with [Ru(η6‐p‐cymene)(μ‐Cl)Cl]2, [Ru(η6‐benzene)(μ‐Cl)Cl]2, [Rh(μ‐Cl)(cod)]2 and [Ir(η5‐C5Me5)(μ‐Cl)Cl]2 gave a range of new monodentate complexes [Ru(Ph2PNHCH2―C4H3O)(η6‐p‐cymene)Cl2] 2, [Ru(Ph2PNHCH2―C4H3O)(η6‐benzene)Cl2] 3, [Rh(Ph2PNHCH2‐C4H3O)(cod)Cl] 4, and [Ir(Ph2PNHCH2‐C4H30)(η5‐C5Me5)Cl2] 5, respectively. All new complexes were fully characterized by analytical and spectroscopic methods. 31P‐{1H} NMR, distortionless enhancement by polarization transfer (DEPT) or 1H‐13C heteronuclear correlation (HETCOR) experiments were used to confirm the spectral assignments. Following activation by KOH, compounds 1, 2, 3, 4 catalyzed the transfer hydrogenation of acetophenone derivatives to 1‐phenylethanol derivatives in the presence of iso‐PrOH as the hydrogen source. Notably [Ru(Ph2PNHCH2‐C4H3O)(η6‐benzene)Cl2] 3 acts as an excellent catalyst, giving the corresponding alcohols in 98–99% yield in 20 min at 82°C (time of flight ≤ 297 h−1) for the transfer hydrogenation reaction in comparison to analogous rhodium or iridium complexes. Copyright © 2012 John Wiley & Sons, Ltd.