Covalent organic frameworks as supports for a molecular Ni based ethylene oligomerization catalyst for the synthesis of long chain olefins

The use of two different classes of covalent organic frameworks (covalent triazine and imine linked frameworks) as supports for molecular Ni²⁺ catalysts is presented. For COFs, a large concentration of N heteroatoms, either in the form of quasi bipyridine or as diiminopyridine moieties, allows for the coordination of NiBr₂ to the scaffold of the porous polymers. When applied as catalysts in the oligomerization of ethylene under mild reaction conditions (15 bar, 50 °C), these new catalysts display an activity comparable to those of their homogeneous counterpart and a fivefold higher selectivity to C₆⁺ olefins. Accumulation of long chain hydrocarbons within the porosity of the COFs leads to reversible deactivation. Full activity and selectivity of the best catalysts can be recovered upon washing with dichlorobenzene.