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Copper‐Mediated Controlled/“Living” Radical Polymerization in Polar Solvents: Insights into Some Relevant Mechanistic Aspects
Author(s) -
Guliashvili Tamaz,
Mendonça Patrícia V.,
Serra Arménio C.,
Popov Anatoliy V.,
Coelho Jorge F. J.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201102183
Subject(s) - disproportionation , polymerization , chemistry , atom transfer radical polymerization , radical polymerization , chelation , polymer chemistry , copper , methyl acrylate , photochemistry , radical , electron transfer , reducing agent , catalysis , combinatorial chemistry , copolymer , organic chemistry , polymer
Abstract The field of transition‐metal‐mediated controlled/“living” radical polymerization (CLRP) has become the subject of intense discussion regarding the mechanism of this widely‐used and versatile process. Most mechanistic analyses (atom transfer radical polymerization (ATRP) vs. single‐electron transfer living radical polymerization (SET‐LRP)) have been based on model experiments, which cannot correctly mimic the true reaction conditions. We present, for the first time, a determination of the [Cu I Br]/[L] (L=nitrogen‐based chelating ligand) ratio and the extent of Cu I Br/L disproportionation during CLRP of methyl acrylate (MA) in dimethylsulfoxide (DMSO) with Cu 0 wire as a transition‐metal catalyst source. The results suggest that Cu 0 acts as a supplemental activator and reducing agent of Cu II Br 2 /L to Cu I Br/L. More importantly, the Cu I Br/L species seem to be responsible for the activation of SET‐LRP.