Electron transfer reactions relevant to atom transfer radical polymerization

The continuous development of more active and stable catalysts in atom transfer radical polymerization (ATRP) has increasingly required a thorough knowledge of concurrent electron transfer reactions that can affect catalyst performance. Special attention is provided in this short review to such processes, including disproportionation, most pronounced in Cu-mediated ATRP, the reduction of radicals to carbanions or oxidation to carbocations, and radical coordination to the metal catalyst resulting in the interplay of controlled radical polymerization mechanisms.

Graphical abstractConcurrent electron transfer reactions that can affect catalyst performance in atom transfer radical polymerization are reviewed, including disproportionation of the Cu catalyst, the reduction of organic radicals to carbanions or oxidation to carbocations, and radical coordination to the metal catalyst.Figure optionsDownload full-size imageDownload as PowerPoint slide