Well-Defined Copper(I) Amido Complex and Aryl Iodides Reacting to Form Aryl Amines

The CuI complex (IPr)Cu(NHPh) {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} reacts with aryl iodides to form diaryl amine products and (IPr)Cu(I), which was confirmed by independent synthesis and characterization. For the reaction with iodobenzene, the products are diphenylamine and aniline. Protection of the hydrogen para to the iodo functionality with ortho-methyl groups results in quantitative conversion to diaryl amine. Combined computational and experimental studies suggest that C−N bond formation most likely occurs via an oxidative addition/reductive elimination sequence.