Nitrosoarene-CuI complexes are intermediates in copper-catalyzed allylic amination

Reactions of nitrosobenzene and N,N'-diethyl-4-nitrosoaniline with Cu(CH3CN)4]PF6 produce novel homoleptic Cu(I)-nitrosoarene complexes, Cu(ArNO)3]PF6, 1 (Ar = Ph) and 2 (Ar = 4-Et2NC6H4NO). The X-ray structure of 2 reveals that the copper is coordinated in a severely distorted trigonal planar geometry to the N-atom of the nitrosoarene ligand. Reactions of the PhNO complex 1 with olefins and an olefin/diene mixture provide evidence for its role as an intermediate and possibly the active nitrogen transfer agent in the Cu-catalyzed allylic amination of olefins by aryl hydroxylamines.