Preparation of Benzyl Azide Complexes of Iridium(III)

Hydride complexes IrHCl2(PiPr3)P2 (1) and IrHCl2P3 (2) [P = P(OEt)3 and PPh(OEt)2] were prepared by allowing IrHCl2(PiPr3)2 to react with phosphite in refluxing benzene or toluene. Treatment of IrHCl2P3, first with HBF4·Et2O and then with an excess of ArCH2N3, afforded benzyl azide complexes [IrCl2(η1-N3CH2Ar)P3]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{η1-NH=C(H)C6H5}P3]BPh4 (5). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [IrCl2(η1-N3CH2C6H5){P(OEt)3}3]BPh4 (3a) and [IrCl2{η1-NH=C(H)C6H5}{P(OEt)3}3]BPh4 (5a). Both solid-state structure and 15N NMR data indicate that the azide is coordinated through the substituted Nγ [Ir]−Nγ(CH2Ar)NNα nitrogen atom.