Catalyzed Radical Termination (CRT) in the Metal-Mediated Polymerization of Acrylates: Experimental and Computational Studies
Résumé
Metal complexes stabilized by appropriate ligands, particularly CuI/L systems, have proven powerful for the controlled polymerization of acrylates and other monomers by atom transfer radical polymerization (ATRP). The polymerization of acrylates by CuI/L systems, however, is haunted by interference of catalyzed radical termination (CRT), which reduces the chain-end fidelity. Other monomers do not appear to be affected by this phenomenon to any significant extent. The phenomenon appears to involve the formation of an organometallic intermediate by reversible radical trapping, as in organometallic mediated radical polymerization (OMRP). We summarize here the current knowledge and the efforts made to elucidate the CRT pathway and products.