Polymer design by organometallic-mediated radical polymerization (OMRP)

Transition metal-assisted polymerization techniques have always played a crucial role in polymer synthesis. As an illustration, metallic compounds have deeply marked the field of living/controlled radical polymerization (L/CRP) which gives access to well-defined polymers under non drastic conditions. Indeed, atom transfer radical polymerization (ATRP) is one of the most successful methods to polymerize vinyl monomers in a controlled manner. Besides this very successful system, another metal-assisted CRP technique is emerging, i.e. organometallic-mediated radical polymerization (OMRP). In contrast to ATRP, OMRP involves the reversible formation of a covalent bond between a transition metal and the polymer chains, which strongly decreases the extent of termination reactions and leads to polymers with predictable molecular weights. This lecture aims to provide a comprehensive overview of the synthetic and mechanistic aspects of OMRP as well as major achievements and remaining challenges in this field.