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Mechanistic studies of transition metal catalyzed radical termination

3rd Edition of International Conference and Exhibition on Polymer Chemistry
March 26-28, 2018 Vienna, Austria

Rinaldo Poli

Institut National Polytechnique, France

Posters & Accepted Abstracts: Polym Sci


Transition metal complexes have proven their utility in macromolecular engineering by catalyzing radical polymerization by atom transfer (ATRP) and also by serving as moderating agents via direct trapping of the growing radical chain to generate organometallic dormant species (OMRP). Certain CuI/L and FeII/L complexes with high ATRP activity have recently been shown to also catalyze radical termination (CRT). The initial interpretation based on work using CuI/L has attributed this phenomenon to the generation of hydride intermediates, H-CuII/L, by �?²-H atom transfer or �?²-H atom elimination from the organometallic dormant species, R-CuII/L. However, more recent mechanistic investigations with L from a family of modified tris(pyridylmethyl)amines (TPMA) with growing donor power, have supported the idea that R-CuII/L is the key CRT intermediate, leading to the termination products upon interaction with a second radical chain and without transit through the hydride H-CuII/L. The intimate mechanism of the R-CuII/L + R reaction to regenerated CuI/L plus termination products, however, is elusive. This presentation will highlight recent experimental and computational investigations that bring light into this matter. Rinaldo.poli@lcc-toulouse.fr