3 research outputs found

    Ethylene Oligomerization beyond Schulz–Flory Distributions

    No full text
    The oligomerization of ethylene produces α-olefin distributions ranging from Schulz–Flory distributions to alternating and selective oligomer distributions that can be mathematically analyzed and characterized by recurrence relations

    Alternating α‑Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

    Get PDF
    The catalytic oligomerization of ethylene with chromium-based complexes containing bis­(benzimidazolemethyl)­amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol<sup>–1</sup> h<sup>–1</sup> bar<sup>–1</sup>) with <i>N</i>-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe<sub>3</sub> and the <i>N</i>-methyl BIMA ligand <b>2</b> have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions

    Alternating α‑Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

    Get PDF
    The catalytic oligomerization of ethylene with chromium-based complexes containing bis­(benzimidazolemethyl)­amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol<sup>–1</sup> h<sup>–1</sup> bar<sup>–1</sup>) with <i>N</i>-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe<sub>3</sub> and the <i>N</i>-methyl BIMA ligand <b>2</b> have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions
    corecore