Abstract

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.

link address：http://onlinelibrary.wiley.com/doi/10.1002/anie.201700546/full