Electron Transfer Reactions in Atom Transfer Radical Polymerization

Electrochemistry may seem an outsider to the field of polymer science and controlled radical polymerization. Nevertheless, several electrochemical methods have been used to determine the mechanism of atom transfer radical polymerization (ATRP), using both a thermodynamic and a kinetic approach. Indeed, electron transfer reactions involving the metal catalyst, initia-tor/dormant species and propagating radicals play a crucial role in ATRP. In this minireview, electrochemical properties of ATRP catalysts and initiators are discussed, together with the mechanism of the atom and electron transfer in ATRP.