Selective ethylene oligomerization with in-situ-generated chromium catalysts supported by trifluoromethyl-containing ligands

A series of pyrrole-containing diarylphosphine and diarylphosphine oxide ligands were prepared. The catalytic activity of the corresponding in-situ-generated chromium catalysts was investigated during selective ethylene oligomerization reactions. Variations in the ligand system were introduced by modifying the diarylphosphine and pyrrole moieties that affect the steric and electronic properties. Minor changes in the ligand structure and the composition of activators significantly changed the catalytic activity, selectivity toward linear alpha-olefins (LAO) versus polyethylene (PE), and the distribution of oligomeric products. The presence of trifluoromethyl groups on the diphenyl rings in ligand 3 promoted oxidation to form the corresponding phosphine oxide structure, 3o, which dramatically enhanced the catalytic activity of ethylene trimerization. The in-situ-generated chromium complex based on 3o activated by DMAO (dry methylaluminoxane)/TIBA (triisobutylaluminum) was used to achieve activity of about 1250 g (mmol of Cr)(-1) h(-1) with 98.5 mol % 1-hexene, along with a negligible amount of PE side product. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 444-450