Phosphine-Phenoxide Nickel Catalysts for Ethylene/Acrylate Copolymerization: Olefin Coordination and Complex Isomerization Studies Relevant to the Mechanism of Catalysis

The insertion copolymerization of ethylene and acrylate remains a challenge in polymer synthesis due to decreased activities upon incorporation of the polar monomer. Toward gaining mechanistic insight, two elusive four-membered chelated intermediates generated after acrylate insertion were prepared (1-CCO and 2-CCO), and their ligand coordination and substitution behavior were studied. Specifically, an ethylene-coordinated species was characterized by NMR spectroscopy upon exposing 2-CCO to ethylene at low temperatures, a rare observation for neutral late-transition metal polymerization catalysts. Thermodynamics of chelate-opening and monomer coordination from 2-CCO were determined at −90 °C (ΔG of 0.4 kcal/mol for ethylene and 1.9 kcal/mol for 1-hexene). The Gibbs energy barrier of ligand exchange from pyridine to ethylene, a prerequisite for ethylene insertion in catalysis, was determined to be 3.3 kcal/mol. Ligand-binding studies reveal that compared to NiMe and Ni­(CH₂SiMe₃) complexes, acrylate inserted species 1L-CCO and 2L-CCO produce compressed thermodynamic binding scales for both electronically and sterically differentiating ligands, potentially related to their more electron-deficient nickel centers as suggested by computational studies. Triethylphosphine complexes 1P, 2P, and 2P–Me were observed as both cis and trans isomers in solution. ³¹P­{¹H} EXSY NMR studies of 2P reveal conversion between a cis and trans isomers that does not involve exchange with free PEt₃, supporting the mechanism of intramolecular isomerization. 2-CCO, a neutral Ni­(II) precatalyst that does not display an auxiliary ligand, serves as a highly active catalyst for copolymerization.