Unexpected Precatalyst σ-Ligand Effects in Phenoxyimine Zr-Catalyzed Ethylene/1-Octene Copolymerizations

Recent decades have witnessed intense research efforts aimed at developing new homogeneous olefin polymerization catalysts, with a primary focus on metal-Cl or metal-hydrocarbyl precursors. Curiously, metal-NR₂ precursors have received far less attention. In this contribution, the Zr-amido complex FI₂ZrX₂ (FI = 2,4-di-tert-butyl-6-((isobutylimino)methyl)phenolate, X = NMe₂) is found to exhibit high ethylene polymerization activity and relatively high 1-octene coenchainment selectivity (up to 7.2 mol%) after sequential activation with trimethylaluminum, then Ph₃C⁺B(C₆F₅)₄^-. In sharp contrast, catalysts with traditional hydrocarbyl ligands such as benzyl and methyl give low 1-octene incorporation (0-1.0 mol%). This unexpected selectivity persists under scaled/industrial operating conditions and was previously inaccessible with traditional metal-Cl or -hydrocarbyl precursors. NMR, X-ray diffraction, and catalytic control experiments indicate that in this case an FI ligand is abstracted from FI₂Zr(NMe₂)₂ by trimethylaluminum in the activation process to yield a catalytically active cationic mono-FIZr species. Heretofore this process was believed to serve only as a major catalyst deactivation pathway to be avoided. This work demonstrates the importance of investigating diverse precatalyst monodentate σ-ligands in developing new catalyst systems, especially for group 4 olefin polymerization catalysts.