Attractive interactions in olefin polymerization mediated by post-metallocene catalysts with fluorine-containing ancillary ligands

The deployment of fluorinated moieties to engender electronic effects through non-covalent attractive interactions is a new concept for olefin polymerization catalysts, and was proposed to account for the unprecedented living polymerization mediated by certain catalysts bearing fluorine-containing ancillary ligands. This strategy is distinct from conventional approaches based on steric influences to control olefin polymerization processes. In this perspective, the concept, generality and beneficial effects of applying non-covalent interactions to control polymerization reactions are discussed, with particular emphasis given to intramolecular C–H⋯F–C interactions between a fluorinated ligand and growing polymer chain.