The binuclear Ni(0) complexes [Ni 2 (μ-CO)(CO) 2 (μ-L 2 ) 2 (3), where L 2 is the bridging diphosphine ligand bis(diphenylphosphino)amine (1H) or bis(diphenylphosphino)methylamine (1Me), have been prepared by the reaction of [Ni(CO) 4 ] and L 2 . The bridging CO ligands in complexes 3 are reversibly displaced by SO 2 yielding [Ni 2 (μ-SO 2 )(CO) 2 (μ-L 2 ) 2 ] (4). The single crystal X-ray structure of the binuclear complex, [Ni 2 (μ-SO 2 )(CO) 2 (μ-(PPh 2 ) 2 NH) 2 ] (4H), is presented. [Ni 2 (μ-SO 2 )(CO) 2 (μ-(Ph 2 -NH) 2 ] (C 8 H 1 0 ) crystallizes in the monoclinic space group C2/c, Z = 4 with lattice parameters a = 27.227(5), b = 9.543(2), c = 22.979(4) 9 and β = 113.26(3)°. Reaction of the complexes 3 with X 2 , where X = Cl or I, ultimately gives [NiX 2 L 2 ] (5), although intermediates in the reactions are observed. 3 1 P NMR and mass spectral data for the complexes are reported. Attempts to react the binuclear complexes 3 with several other ligands were unsuccessful.