MOF-Supported Diimine-Ni Catalyzed Highly Active Propylene Dimerization

Abstract

A heterogeneous diimine-Ni catalyst (diimine-Ni@PCN-701) is synthesized through sequential ligand insertion into PCN-700, a robust Zr-based metal-organic framework (MOF), followed by chelation of Ni centers. This site-specific assembly affords a robust active center for propylene dimerization with superior activity, which arises from the electron-withdrawing effect of Zr₆O₄(OH)₄ clusters on the Ni active sites. Propylene is selectively converted into a series of dimers with 4-methyl-2-pentene (4M2P) as the main product, which may be due to the MOF structure promoting this reaction through both electronic effects and steric hindrance. This work highlights a general strategy for developing heterogeneous olefin oligomerization catalysts with high activity and shape selectivity through the precise construction of active sites.

Keywords

heterogeneous catalyst / metal-organic framework (MOF) / diimine-Ni complex / propylene dimerization

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Funding

National Natural Science Foundation of China(22071023)

National Natural Science Foundation of China(22101056)

Program of Shanghai Academic and Technology Research Leader, China(22XD1400100)

Fundamental Research Funds for the Central Universities, China(2232020A-05)

National Natural Science Foundation of China(2232024D-04)