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Organometallic‐Mediated Radical Polymerization: Developing Well‐Defined Complexes for Reversible Transition Metal‐Alkyl Bond Homolysis
Author(s) -
Smith Kevin M.,
McNeil W. Stephen,
AbdElAziz Alaa S.
Publication year - 2010
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200900581
Subject(s) - chemistry , polymerization , homolysis , alkyl , polymer chemistry , radical polymerization , cobalt mediated radical polymerization , photochemistry , methylaluminoxane , transition metal , living free radical polymerization , catalysis , polymer , organic chemistry , radical , metallocene
Organometallic‐mediated radical polymerization (OMRP) has emerged as a powerful new class of living controlled radical polymerization. In order to fulfill its potential in the polymerization of vinyl acetate (VOAc) and other challenging monomers, the effects of ancillary ligands on the metal‐alkyl bond dissociation energy in OMRP reagents must be thoroughly explored. Recent results investigating structure‐activity relationships in well‐defined cobalt, iron and chromium complexes will be discussed. The involvement of radical intermediates in oxidative addition of secondary alkyls for catalytic cross‐coupling reactions catalyzed by first row transition metals will also be examined for relevant design concepts.