Acrylate-Induced β-H Elimination in Coordination Insertion Copolymerizaton Catalyzed by Nickel.

Polar monomer-induced β-H elimination is a key elementary step in polar polyolefin synthesis by coordination polymerization but remains underexplored. Herein, we show that a bulky neutral Ni catalyst, , is not only a high-performance catalyst in ethylene/acrylate copolymerization (activity up to ∼37,000 kg/(mol·h) at 130 °C in a batch reactor, mol % tBA ∼ 0.3) but also a suitable platform for investigation of acrylate-induced β-H elimination.

Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene-Acrylate Copolymers.

The insertion copolymerization of polar olefins and ethylene remains a significant challenge in part due to catalysts' low activity and poor thermal stability. Herein we demonstrate a strategy toward addressing these obstacles through ligand design. Neutral nickel phosphine enolate catalysts with large phosphine substituents reaching the axial positions of Ni achieve activity of up to 7.