Mechanism of Cu(I)/Cu(0)-Mediated Reductive Coupling Reactions of Bromine-Terminated Polyacrylates,...

The mechanism of the Cu(I)/Cu(0)-mediated reductive coupling reactions of bromine-terminated polymer chain-end radicals, so-called atom-transfer radical coupling (ATRC), is studied. Poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), and polystyrene (PSt), prepared by atom-transfer radical polymerization (ATRP), were activated by an excess amount of Cu(I)Br and Cu(0) in the presence of tris[2-(dimethylamino)ethyl]amine (Me₆TREN), and the structural analyses of the resulting polymer products and deuterium-labeling experiments unambiguously determined the mechanism. While PMMA and PSt reacted by a radical mechanism as expected, PMA-bromide was reduced to an anionic species, which was most likely an organocopper species. Trapping experiments with TEMPO suggested that the polymer chain-end radicals were generated in all cases by the reduction of the bromine-terminated polymers by low-valent Cu species. However, the PMA chain-end radical was further reduced to the anionic species from which coupling products formed in low yield.