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

Abstract

Imine complexes [IrCl(η5‐C5Me5){κ1‐NH=C(H)Ar}{P(OR)3}]BPh4 (1, 2) (Ar = C6H5, 4‐CH3C6H4; R = Me, Et) were prepared by allowing chloro complexes [IrCl2(η5‐C5Me5){P(OR)3}] to react with benzyl azides ArCH2N3. Bis(imine) complexes [Ir(η5‐C5Me5){κ1‐NH=C(H)Ar}2{P(OR)3}](BPh4)2 (3, 4) were also prepared by reacting [IrCl2(η5‐C5Me5){P(OR)3}] first with AgOTf and then with benzyl azide. Depending on the experimental conditions, treatment of the dinuclear complex [IrCl2(η5‐C5Me5)]2 with benzyl azide yielded mono‐ [IrCl2(η5‐C5Me5){κ1‐NH=C(H)Ar}] (5) and bis‐[IrCl(η5‐C5Me5){κ1‐NH=C(H)Ar}2]BPh4 (6) imine derivatives. In contrast, treatment of chloro complexes [IrCl2(η5‐C5Me5){P(OR)3}] with phenyl azide C6H5N3 gave amine derivatives [IrCl(η5‐C5Me5)(C6H5NH2){P(OR)3}]BPh4 (7, 8). The complexes were characterized spectroscopically (IR, NMR) and by X‐ray crystal structure determination of [IrCl(η5‐C5Me5){κ1‐NH=C(H)C6H4‐4‐CH3}{P(OEt)3}]BPh4 (2b).