The reactions of nitrosobenzene and N,N'-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6 provide novel Cu(I) complexes, [Cu(PhNO)3]PF6 (1) and [Cu(Et2NPhNO)3]PF6 (2); in 2 the copper atom is N-coordinated to the nitrosoarenes in a distorted trigonal planar geometry VSports手机版. Complex 1 is strongly implicated as a reactive intermediate in the Cu(I)-catalyzed allylic amination of olefins based on (i) its isolation from the catalytic reaction, (ii) its stoichiometric regioselective allylic amination of alpha-methyl styrene (AMS), (iii) the non-involvement of free PhNO in its amination of AMS, and (iv) its function as a catalyst for the amination of alkenes from phenylhydroxylamine. The reaction between AMS and 1 (80 degrees C, dioxane) is first order in both alkene and 1. Relative rate studies of the reaction of 1 with para substituted AMS derivatives gives a Hammett rho value of -0. 035. Alkene adducts isolated from the reaction of 1 with styrene and alpha-methylstyrene are formulated as [(PhNO)3Cu(eta(2)-alkene)]PF6 (7,8) on the basis of spectroscopic characterization and thermolysis. PM3 and DFT MO calculations support the role of [(alkene)Cu(RNO)3]+ and (eta(1)- or eta(3)-allyl)Cu(RNO)2(RNHOH)+ complexes as probable catalytic intermediates and address the origin of the distinctive reaction regioselectivity. A mechanistic scheme is proposed which is consistent with the accumulated experimental and computational results. .