Coordination of aniline to an (eta(1)-allenyl)iridium complex leading to hydroanilination

Formation of the N-arylated eta(3)-aza-TMM complexes of iridium from regioselective hydroanilination of an octahedral (eta(1)-allenyl)iridium complex has been studied. (OC-6-42)-Ir(Cl)(PPh(3))(2)(OTf)(CO)(eta(1)-CHCCH2) (2) undergoes the substitution of L (L = NH3, NH2NH2, MeNH(2), EtNH(2), (PrNH2)-Pr-i, PhCH(2)NH(2)) for the triflate ligand to yield {(OC-6-42)-Ir(Cl)(PPh(3))(2)-(L)(Co)(eta(1)-CHCCH2)}(OTf) (3d-i). In contrast, the reactions of 2 with XC(6)H(4)NH(2) (X = F, NO2, MeO, H, Me), Ph(2)NH, and Ph(Me)NH result in regioselective addition at the allenyl ligand, thereby generating the N-arylated eta(3)-aza-TMM complexes 5a-g. The mechanistic studies confirm that the hydroanilination is preceded by the formation of an aniline-ligated intermediate.