Thermal reaction of [H₃Mn₃(CO)₁₂] with Ph₂PC₆H₄NH₂-2 gives good yields of [Mn₂(CO)₆(PPh₂C₆H₄NH)₂], an X-ray single crystal structure determination of which reveals a P,N-chelating ligand with each of the NH groups, formed by deprotonation of the amine groups, bridging the two metal atoms.