A new family of iridium (III) anionic complexes {Li [Ir (P–P) I4]; P–P= 1, 2-bis (diphenylphosphino) ethane, cis-1, 2-bis (diphenylphosphino) ethylene, and R-(+)-1, 2-bis (diphenylphosphino) propane} has been synthesised; they are efficient for catalytic and chemoselective hydrogenation of aldimines and ketimines at 20° C and 25 bar H2 (1 bar= 105 Pa).