Reactions of Organic Azides with Half-sandwich Complexes of Iridium: Preparation of Mono- and Bis(imine) Derivatives: Reactions of Organic Azides with Half-sandwich Complexes of Iridium: Preparation of Mono- and Bis(imine) Derivatives

Imine complexes [IrCl(eta (5)-C5Me5){kappa (1)-NH=C(H)Ar}{P(OR)(3)}]BPh4 (1, 2) (Ar = C6H5, 4-CH3C6H4; R = Me, Et) were prepared by allowing chloro complexes [IrCl2(eta (5)-C5Me5){P(OR)(3)}] to react with benzyl azides ArCH2N3. Bis(imine) complexes [Ir(eta (5)-C5Me5){kappa (1)-NH=C(H)Ar}(2){P(OR)(3)}](BPh4)(2) (3, 4) were also prepared by reacting [IrCl2(eta (5)-C5Me5){P(OR)(3)}] first with AgOTf and then with benzyl azide. Depending on the experimental conditions, treatment of the dinuclear complex [IrCl2(eta (5)-C5Me5)](2) with benzyl azide yielded mono- [IrCl2(eta (5)-C5Me5){kappa (1)-NH=C(H)Ar}] (5) and bis-[IrCl(eta (5)-C5Me5){kappa (1)-NH=C(H)Ar}(2)]BPh4 (6) imine derivatives. In contrast, treatment of chloro complexes [IrCl2(eta (5)-C5Me5){P(OR)(3)}] with phenyl azide C6H5N3 gave amine derivatives [IrCl(eta (5)-C5Me5)(C6H5NH2){P(OR)(3)}]BPh4 (7, 8). The complexes were characterized spectroscopically (IR, NMR) and by X-ray crystal structure determination of [IrCl(eta (5)-C5Me5){kappa (1)-NH=C(H)C6H4-4-CH3}{P(OEt)(3)}]BPh4 (2b).