Two complexes of the pseudohalide nitrosodicyanomethanide, [ONC(CN)(2)](-), with Fe-III(TTP)[ONC(CN)(2)], 1, and Ir-I[ONC(CN)(2)](CO)(PPh(3))(2), 2, have been prepared and characterized by single-crystal X-ray crystallography, elemental analysis, electrochemistry, and IR, NMR, UV-vis, and ESR spectroscopy. This pair of complexes illustrates the ambidentate nature of the nitrosodicyanomethanide ligand. Ab initio calculations with Gaussian92 are used to rationalize the observed oxygen binding to iron in 1 and nitrogen binding to the iridium in 2. The single-crystal X-ray diffraction results include the following : 1, triclinic space group P ($) over bar 1, a = 11.725(2) Angstrom A, b = 13.851(3) Angstrom A, c = 14.382(3) Angstrom A, alpha = 108.74(3)degrees, beta = 95.07(3)degrees, gamma = 108.19(3)degrees, Z = 2; 2, triclinic space group P ($) over bar 1, a = 12.662(3) Angstrom A, b = 13.896(3) Angstrom A, c = 21.879(4) Angstrom A, alpha = 74.69(3)degrees, beta = 78.65(3)degrees, gamma = 83.10(3)degrees, Z = 4.