White crystals of Fe((OPPh2)2N)3 were obtained from the reaction of a solution of Fe2(CO)9 and excess (PPh2)2NH, under an air atmosphere. This product does not form if the solvents are rigorously degassed and the reaction is performed under argon. The structure of the complex, as determined by single crystal X-ray crystallography, is an octahedral tris-chelate arrangement of the oxidized anionic ligand, [(O=PPh2)2N]− coordinated to an Fe(III) center. The asymmetric unit of the unit cell also contains a disordered THF solvent molecule. The complex crystallizes in the triclinic space group P1, with Z = 2, a = 13.581(3), b = 13.886(8), c = 18.781(7) Å, α = 95.48(4), β = 98.73(2), γ = 97.82(3)°, V = 3444(2) Å3, Mr = 1377, Dx = 1.33 Mg m−3, F(000) = 1434, T = 298 K and R = 0.086 for 5959 observed reflections. The magnetic moment of the compound Fe((OPPh2)2N)3 was found to be 5.4 BM, using the Gouy method. Reaction of the oxidized ligand, (OPPh2)2NH, with Fe(III) salts, such as Fe(NO3)3, produces Fe((OPPh2)2N)3 in high yields.