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Chromium complexes bearing a series of pyridine–phosphine ligands have been synthesized and examined for their catalytic behavior in ethylene oligomerization. The choice of solvent, toluene versus methylcyclohexane, shows a pronounced influence on the catalytic activity for all these complexes. Variations of the ligand system have been introduced by modifying the phosphine substituents affecting ligand bite angles and flexibility. It has been demonstrated that minor differences in the ligand structure can result in remarkable changes not only in catalytic activity but also in selectivity toward α-olefins versus polyethylene and distribution of oligomeric products. Ligand PyCH2N(Me)PiPr2, in combination with CrCl3(THF)3 afforded selective ethylene tri- and tetramerization, giving 1-hexene and 1-octene with good overall selectivity and high purity, albeit with the presence of small amounts of PE.

Selective Ethylene Oligomerization with Chromium Complexes Bearing Pyridine–Phosphine Ligands: Influence of Ligand Structure on Catalytic Behavior