The reaction of Ir2Cl2(CO)(2)(mu-dppm)(2) (dppm = bis(diphenylphosphino)methane) With 2 equiv of LiNHR yields Ir-2(mu-NR)(CO)(2)(mu-dppm)(2), 1 (R = p-tolyl, Ph, p-BrC6H4, p-NO2C6H4), or its tautomer Ir-2(mu-NHR)(CO)(2)(mu-dppm)-(mu-dppm-H), 2 (dppm-H = bis(diphenylphosphino)methanide; R = Et, Bu(t)). NMR data suggest that 1 (R = p-tolyl, Ph, p-BrC6H4) are in equilibrium with small amounts of 2 in polar solvents. An X-ray structural determination of 1 (R = p-tolyl) shows that the imido nitrogen atom links two iridium atoms at the apex of an A-frame complex. A very short N-C distance in the imido group suggests extensive N-lone pair donation to the tolyl ring. Crystals of 1 (R p-tolyl) from benzene are tetragonal (P4(3)) with a 21.337(1) Angstrom, c = 14.478-(2) Angstrom, and Z = 4. With the exception of R = p-NO2C6H4, p-BrC6H4, and Et, the complexes react with 1 equiv of CO at ambient temperature to form Ir-2(CO)(3)(mu-dppm)(2) as the major metal containing product. For R = Et, the reaction generates the unstable isocyanate complex Ir-2(mu-EtNCO)(CO)(2)(mu-dppm)(2). All of the complexes react with excess CO (2 atm) yielding Ir-2(CO)(4)(mu-dppm)(2) and amine except for the p-NO2C6H4 complex, which gives a complex mixture of products.