Hydride complexes IrHCl2((PPr3)-Pr-i)P-2 (1) and IrHCl2P3 (2) [P = P(OEt)(3) and PPh(OEt)(2)] were prepared by allowing IrHCl2((PPr3)-Pr-i)(2) to react with phosphite in refluxing benzene or toluene. Treatment of IrHCl2P3, first with HBF4 center dot Et2O and then with an excess of ArCH2N3, afforded benzyl azide complexes [lrCl2(eta(1)-N3CH2Ar)P-3]BPh4 (3, 4) [Ar = C6H5, 4-CH3C6H4; P = P(OEt)(3), PPh(OEt)(2)]. Azide complexes reacted in CH2Cl2 solution, leading to the imine derivative IrCl2{eta(1)-NH=C(H)C6H5}P-3]BPh4 (5). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [IrCl2(eta(1)-N3CH2C6H5){P(OEt)(3)}(3))BPh4 (3a) and [IrCl2{eta(1)-NH=C(H)C6H5}{P(OEt)(3)}(3)]-BPh4 (5a). Both solid-state structure and N-15 NMR data indicate that the azide is coordinated through the substituted N gamma [Ir]-N gamma(CH2Ar)NN alpha nitrogen atom.