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<p>This study establishes molecular design principles for bis(imino)pyridine cobalt catalysts to simultaneously enhance activity and 1-hexene selectivity in propylene oligomerization. Systematic substituent engineering revealed: (1) <i>para</i>-Halogenation (e.g., Br in <b>4d</b>) boosts activity to high levels (4.68 × 10⁵ g/(mol<sub>(Co)</sub>·h)) through electronic effects; (2) <i>ortho</i>-Steric modulation follows a volcano-shaped selectivity trend, with isopropyl groups optimizing 1-hexene formation; (3) Conversion control is critical for suppressing secondary reactions that compromise selectivity. Implementing these insights, catalyst <b>4L</b> achieves 56.1% 1-hexene selectivity at low conversions (10.4%). These findings provide a blueprint for developing high-performance cobalt oligomerization catalysts through integrated electronic, steric, and process optimization.</p> Graphical Abstract <p></p>

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Steric and Electronic Tuning of Bis(imino)pyridine Cobalt Catalysts for High 1-Hexene Selectivity in Conversion-Controlled Propylene Oligomerization

  • 期刊论文

  • 发表日期：

    2026年2月12日

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  • Jialei Gao,
  • Zhi Luo,
  • Zhong-Hua Gao,
  • Huayi Li,
  • Song Ye

摘要

This study establishes molecular design principles for bis(imino)pyridine cobalt catalysts to simultaneously enhance activity and 1-hexene selectivity in propylene oligomerization. Systematic substituent engineering revealed: (1) para-Halogenation (e.g., Br in 4d) boosts activity to high levels (4.68 × 10⁵ g/(mol(Co)·h)) through electronic effects; (2) ortho-Steric modulation follows a volcano-shaped selectivity trend, with isopropyl groups optimizing 1-hexene formation; (3) Conversion control is critical for suppressing secondary reactions that compromise selectivity. Implementing these insights, catalyst 4L achieves 56.1% 1-hexene selectivity at low conversions (10.4%). These findings provide a blueprint for developing high-performance cobalt oligomerization catalysts through integrated electronic, steric, and process optimization.

Graphical Abstract