2-Benzimidazol-6-pyrazol-pyridine Chromium(III) Trichlorides: Synthesis, Characterization, and Application for Ethylene Oligomerization and Polymerization

Abstract

A series of chromium(III) complexes, LCrCl3 (Cr1–Cr4: L = 2-(N-R2-benzimidazol-2-yl)-6-(3,5-R1-pyrazol-1-yl)pyridine; Cr1: R1 = H, R2 = H; Cr2: R1 = Me, R2 = H; Cr3: R1 = Me, R2 = Me; Cr4: R1 = Me, R2 = Bn), were synthesized and characterized by IR spectroscopy and elemental analysis. The studies of the solid state of Cr2 and Cr3 revealed distorted octahedral geometries around the chromium centers by X-ray diffractions. In the presence of MAO, Cr1–Cr4 exhibited high activities toward ethylene oligomerization (up to 2.17 × 106 g·mol–1(Cr)·h–1) and ethylene polymerization (up to 6.78 × 105 g·mol–1(Cr)·h–1). The oligomers were produced with high selectivity for α-olefins (>99%), confirmed by FT-IR and 13C NMR, and the distributions followed the Schulz–Flory equation. Various reaction parameters including the amount of cocatalyst, reaction temperature, and time were evaluated in detail, and it was evident that the title complexes had good thermal stability and the substituents on imidazole-N of the ligands dramatically impacted the catalytic activities as well as the distribution of the products.