Mechanistic Insights into the cis-Selective Catalytic Ring-Opening Metathesis Polymerization

Cis-selective ring-opening metathesis polymerization (ROMP) with the commercial Grubbs "nitrato catalyst" has shown promise for synthesizing stereoregular materials, but it comes with the drawback of losing control over the molecular weight due to the poor initiation rate of the catalyst and the need for stoichiometric ruthenium complex loading. To address these issues, we developed a chain transfer polymerization method that allows for the catalytic synthesis of polymers while controlling the degree of polymerization. This allowed us to produce shorter polymers with exceptional chain-end control. Analysis of the polymers revealed a novel double monomer addition mechanism for this catalyst. MALDI-ToF mass spectrometric measurements showed that when using small monomers like norbornene, the polymer chains contained only odd numbers of monomers. In contrast, the polymerization of norbornene-imide-type monomers shows a major distribution with odd numbers of monomers along with a minor distribution of even numbers. This unique distribution of polymer chain types had not been previously observed in ROMP. We explain this phenomenon by the chiral nature of the catalyst that yields two isomeric catalytic species with dissimilar reactivities toward monomer and chain transfer agents.