Coordination of Aniline to an (η1-Allenyl)iridium Complex Leading to Hydroanilination

Formation of the N-arylated η 3 -aza-TMM complexes of iridium from regioselective hydroanilination of an octahedral (η 1 -allenyl)iridium complex has been studied. ( OC -6-42)-Ir(Cl)(PPh 3 ) 2 (OTf)(CO)(η 1 -CHCCH 2 ) ( 2 ) undergoes the substitution of L (L = NH 3, NH 2 NH 2, MeNH 2, EtNH 2, i PrNH 2, PhCH 2 NH 2 ) for the triflate ligand to yield {( OC -6-42)-Ir(Cl)(PPh 3 ) 2 (L)(CO)(η 1 -CHCCH 2 )}(OTf) ( 3d−i ). In contrast, the reactions of 2 with XC 6 H 4 NH 2 (X = F, NO 2, MeO, H, Me), Ph 2 NH, and Ph(Me)NH result in regioselective addition at the allenyl ligand, thereby generating the N-arylated η 3 -aza-TMM complexes 5a−g . The mechanistic studies confirm that the hydroanilination is preceded by the formation of an aniline-ligated intermediate.