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

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