The reaction of [Ir(cod)(μ-Cl)]₂ (cod=1,5-cyclooctadiene) with 2 equiv of the ketophosphine Ph₂PCH₂C(O)Ph in the presence of TlPF₆ afforded the hydrido, phosphino-enolate Ir(III) complex [IrH(cod){Ph₂PCH···C(···O)Ph,κP,κO}{Ph₂PCH₂C(O)Ph,κP}]PF₆ (4), which results from the room temperature activation of a C–H bond from the PCH₂ moiety. The distorted octahedral coordination environment around the metal centre in 4 contains the cod ligand, the P atom of the monodentate ketophosphine and the P,O donor atoms of a chelating phosphino-enolate ligand acting as a 3-electron donor. The hydride ligand was located on the difference Fourier map obtained by single-crystal X-ray diffraction studies and is trans to the enolate oxygen and cis to the two, mutually cis P atoms. The reaction of this complex with NaH in THF led to the isolation of the Ir(I) complex [Ir(cod){Ph₂PCH···C(···O)Ph,κP,κO}{Ph₂PCH₂C(O)Ph,κP}] (5). The penta-coordination environment around the metal centre in 5 includes the cod ligand, one 3-electron donor P,O chelating phosphino-enolate ligand and a P-bound Ph₂PCH₂C(O)Ph ligand containing an uncoordinated ketone function. The structures of 4·CH₂Cl₂ and 5·C₇H₈ have been determined by X-ray diffraction analysis.