Coordination Polymerization of Renewable 3-Methylenecyclopentene with Rare-Earth-Metal Precursors

Coordination polymerization of renewable 3-methylenecyclopentene has been investigated for the first time using rare-earth metal-based precursors bearing various bulky ligands. All the prepared complexes catalyze controllable polymerization of 3-methylenecyclopentene into high molecular weight polymers, of which the NPN- and NSN-tridentate non-Cp ligated lutetium-based catalytic systems exhibited extremely high activities up to 11 520 kg/(mol_Lu ⋅h) in a dilute toluene solution (3.2 g/100 mL) at room temperature. The resultant polymers have pure 1,4-regioregularity (>99 %) and tailorable number average molecular weights (1-20×10⁴ ) with narrow molecular weight distributions (polydispersity index (PDI)=1.45-1.79). DFT simulations were employed to study the polymerization mechanism and stereoregularity control.