Mechanistic Insights into Alkene Chain Growth Reactions Catalyzed by Nickel Active Sites on Ordered Microporous and Mesoporous Supports

Alkene oligomerization on heterogeneous Ni-based catalysts has been studied for several decades, with recent attention focused on the preparation, structure and function of Ni active site motifs isolated within microporous and mesoporous supports, including zeolites and metal-organic frameworks (MOFs). This mini-review focuses on the active site requirements and the microscopic kinetic and mechanistic details that become manifested macroscopically as activation and deactivation behavior during oligomerization catalysis, and that determine measured reaction rates and selectivity among alkene isomer products. The preponderance of mechanistic evidence is consistent with the coordination-insertion (Cossee-Arlman) cycle for alkene oligomerization prevailing on heterogeneous Ni-exchanged zeolites and MOFs, even when external co-catalysts are not present, as they often are in homogeneous Ni-based oligomerization catalysis. Certain mechanistic features of the coordination-insertion route allow catalyst and active site design strategies to influence product selectivity. Our mini-review provides a critical discussion of reported alkene oligomerization data and the challenges in their measurement and interpretation, and concludes with an outlook for future research opportunities to improve our kinetic and mechanistic understanding of alkene chain growth chemistries mediated by Ni-based porous catalysts.