The bridging amido ligands in Ir-2[mu-NH(p-tolyl)](2)(CO)4, 1, undergo deprotonation by ’BuLi in a stepwise manner. The first deprotonation product is a monoanionic mu-amido/mu-imido complex of formula LiIr2[mu-NH(p-tolyl)][mu-N(p-tolyl)](CO)(4).2THF, 2, which shows three CO bands in the IR, similar to the pattern observed for 1. However, the bands are shifted to lower energy by an average of similar to 50 cm(-1). The second deprotonation step produces a dianionic bis(mu-imido) complex, Li2Ir2[mu-N(p-tolyl)](2)(CO)4.3THF, 3, in which the CO bands are shifted by another 25 cm(-1)(average). The high solubility of the ionic complexes in hydrocarbon solvents, coupled with the number of THF molecules available for each lithium ion, suggests strong cation-anion interaction, most likely at the imido nitrogens. Variable-temperature NMR studies have detected the formation of aggregates in solution for 2. Complex 3 possesses two inequivalent lithium ions that produce separate Li-7 signals at temperatures below 0 degrees C but produce an average signal around room temperature. The THF molecules in 2 and 3 can be displaced by 12-Crown-4 to give complexes 2.Crown and 3.Crown, in which the lithium ions are encapsulated by the crown ether. The reaction of 3 with (PPh(3))AuCl generates a tetranuclear complex, [(CO)(2)Ir(mu-N(p-tolyl))Au(PPh(3))](2), 4.