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Nitrosoarene−Cu(I) Complexes Are Intermediates in Copper-Catalyzed Allylic Amination

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journal contribution
posted on 25.05.2005, 00:00 by Radhey S. Srivastava, Masood A. Khan, Kenneth M. Nicholas
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.