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Radical Coordination Chemistry and Its Relevance to Metal‐Mediated Radical Polymerization
Author(s) -
Poli Rinaldo
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201001364
Subject(s) - chemistry , radical , polymerization , atom transfer radical polymerization , radical polymerization , cobalt mediated radical polymerization , photochemistry , coordination sphere , living free radical polymerization , polymer chemistry , nitroxide mediated radical polymerization , chain transfer , metal , reversible addition−fragmentation chain transfer polymerization , organic chemistry , polymer
The reactions engaged by organic radicals with transition‐metal complexes are reviewed with a particular focus on how they can interplay with and affect the results of radical polymerization. Radicals can either add to a metal centre to establish metal–carbon bonds, abstract an atom or group, be abstracted by an atom or group, undergo associative exchange, transfer a β‐H atom or add to existing ligands in the metal coordination sphere. Reversibility is key for certain controlled polymerization methods. The various ways in which metal complexes can play a role in radical polymerization lead to atom‐transfer radical polymerization (ATRP), organometallic‐mediated radical polymerization by either reversible termination (OMRP‐RT) or degenerative transfer (OMRP‐DT) and chain‐transfer‐catalysed radical polymerization (CTCRP).