Organometallic-Mediated Radical Polymerization: Developing Well-Defined Complexes for Reversible Transition Metal-Alkyl Bond Homolysis

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.