Efficient MOF-Based Catalyst for the Selective Ethylene Dimerization
Résumé
Post-synthetic modification is a powerful tool for obtaining highly sophisticated functionalized structures. It consists in the introduction of functionalities after framework synthesis and allows the preparation of MOF-supported organometallics usually through two-steps modification to introduce first covalently the coordinating ligand and then form the metal complex. We report here the first one-pot combined covalent-dative MOF post-functionalization leading to the grafting of a nickel-based organometallic catalyst within the framework of (Fe)MIL-101-NH2 under mild conditions.[1] This is the first example of the covalent synthesis of a MOF-supported bipyridine-like ligand simultaneously coordinated by a metal precursor, here a nickel salt. This one-pot methodology offers advantages of avoiding both the interactions of the coordinating moiety with the metal nodes and the pore blocking with metal clusters. Furthermore these Ni-functionalized MOFs act as very active, reusable and cost-competitive catalysts for the ethylene oligomerization in the liquid phase with intrinsic activities up to 10455h-1 and a high selectivity towards 1-butene.