H-Bonding leading to latent initiators for olefin metathesis polymerization

Ruthenium-NHC based catalysts, with a chelated iminium ligand trans to the N-heterocyclic carbene (NHC) ligand, that polymerize dicyclopentadiene (DCPD) at different temperatures are monitored using Density Functional Theory calculations to unveil the reaction mechanism, and subsequently how important are the geometrical and electronic features vs. the non-covalent interactions in between. The balance is very fragile and H-bonds are fundamental to explain the different behaviour of latent catalysts. This computational study aims to facilitate future studies of new generations of latent initiators for olefin metathesis polymerization, with the 3D and mainly the 2D Non-Covalent Interaction plots the characterization tool for H-bonds.

Automated summary

Ruthenium-NHC based catalysts with chelated iminium ligand were studied using Density Functional Theory calculations to understand the reaction mechanism of dicyclopentadiene polymerization at different temperatures. The importance of geometrical and electronic features, as well as non-covalent interactions, especially H-bonds, were investigated. This computational study aims to facilitate future research on new generations of latent initiators for olefin metathesis polymerization using Non-Covalent Interaction plots as a characterization tool for H-bonds.