REACTION OF ORGANIC HALIDES WITH [CU(I)(TMPA)CH3CN]PF6

Under mild conditions, the copper(I) complex [Cu1(TMPA)CH3CN]PF6 (TMPA = tris(2-pyridylmethyl)amine), reacts stoichiometrically with benzyl and allyl halides, and alpha-halo-ketones to produce near quantitative yields of carbon-carbon reductively coupled products bibenzyls, diolefins or diketones, respectively. The copper complex acts as the halide acceptor and the copper(II) complex [Cu(II)(TMPA)X]PF6 (X = Cl- or Br-) is also isolated. No firm mechanistic conclusions can be drawn, but the intermediacy of oxidatively added RX products, i.e. organo-Cu(II) or Cu(III), is suggested.