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Five examples of selectively fluorinated unsymmetrical diiminoacenaphthylenes, 1-[2,6-{(4-FC 6 H 4 ) 2 CH} 2 -4-FC 6 H 4 N]-2-(ArN) C 2 C 10 H 6 (Ar = 2,6-Me 2 C 6 H 3 L1, 2,6-E 2 C 6 H 3 L2, 2,6-iPr 2 C 6 H 3 L3, 2,4,6-Me 3 C 6 H 2 L4, 2,6-E 2 -4-MeC 6 H 2 L5), have been synthesized and used to prepare their corresponding nickel(ii) halide complexes, LNiBr 2 (Ni1-Ni5) and LNiCl 2 (Ni6-Ni10). Both 1 H and 19 F NMR spectroscopy techniques have been employed to characterize paramagnetic Ni1-Ni10; an inequivalent fluorine environment is a feature of the tetrahedral complexes in solution. Upon activation with relatively low ratios (ca. 600 equiv.) of ethylaluminum sesquichloride (E 3 Al 2 Cl 2 , EASC), all the nickel complexes displayed high activities toward ethylene polymerization at 30 °C with precatalyst Ni4 the standout performer at 2.20 × 10 7 g of PE per mol of Ni per h, producing highly branched polyethylenes. In comparison with related diiminoacenaphthylene-nickel catalysts, these current systems, incorporating a high fluorine content on one N-aryl group, display superior productivity. In addition, the molecular structures of Ni2 and Ni4 are reported and the active catalyst is probed using 19 F NMR spectroscopy.

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Raising the N-aryl fluoride content in unsymmetrical diaryliminoacenaphthylenes as a route to highly active nickel(<scp>ii</scp>) catalysts in ethylene polymerization

Raising the N-aryl fluoride content in unsymmetrical diaryliminoacenaphthylenes as a route to highly active nickel(ii) catalysts in ethylene polymerization