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Several new halfsandwich rutheniumII complexes containing 2diphenyphosphanylaniline PNH2 of formula {Ru[κ2P,NPNH2]pcymeneCl}Y [Y = Cl 1a, PF61b, BF41c, BPh41d, TfO 1e] were synthesized and fully characterized both in solution 1H NMR and 31P{1H} NMR spectroscopy and in the solid state FTIR, Xray analysis on single crystal. Complexes 1aand 1bare active precatalysts in the hydrogen transfer reaction of acetophenone, leading to tof values up to 4440 h–1. In comparison, the {Ru[κ2P,NPNMe2]pcymeneCl}Cl complex leads to a tof value of 100 h–1under the same catalytic conditions. The mechanism through which the precatalysts operate was deeply explored by highresolution MS ESI and DFTPCM studies. The results reveal that the complexes containing PNH2operate through a bifunctional mechanism analogous to that proposed for diamines and amino alcohol ligands. © WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008