Novel Dendritic PNP Chromium Complexes: Synthesis, Characterization, and Performance on Ethylene Oligomerization

Three dendritic PNP ligands with ethylenediamine, 1,4-butanediamine, 1,6-diaminohexane as bridged groups are synthesized in good yields, respectively. Three dendritic PNP chromium complexes (C1-C3) are prepared with the ligands and chromium(III) chloride tetrahydrofuran complex (CrCl3(THF)(3)) as materials. The dendritic PNP ligands and the synthetic chromium complexes are fully characterized by spectroscopic and analytical methods. All chromium complexes activated with methylaluminoxane (MAO) exhibited moderate activities on ethylene oligomerization (7.90x10(4)-2.15x10(5)g(molCrh)(-1)] and had better selectivity for C-6 and C-8 oligomer, reaching up to 81%. The chromium complex (C1) activated with diethylaluminium chloride (Et2AlCl) has higher catalytic activity than the chromium complex C1 activated with MAO, although the chromium complex (C1) activated with Et2AlCl had lower selectivity for C-6 and C-8 oligomer. The effects of solvent and reaction parameters on ethylene oligomerization are also studied using the chromium complex C1 as pre-catalyst and MAO as co-catalyst. Under optimized conditions ([complex]=2mol, Al/Cr=500, 25 degrees C, 0.9 MPa ethylene, 30min), the catalytic activity of complex C1 in toluene is 2.15x10(5)g(molCrh)(-1) and the selectivity for C-6 and C-8 oligomer is 36.76%. In addition, the structure of complexes significantly affects both the catalytic activity and the selectivity on ethylene oligomerization.