New chromium complexes for ethylene oligomerization: Extended use of tridentate ligands in metal-catalyzed olefin polymerization

A family of chromium complexes bearing tridentate pyridine-based ligands are disclosed as highly active precatalysts for the oligomerization of ethylene. The ligands are comprised of two distinct types: Type 1, in which both ketone groups of 2,6-diacetylpyridine are converted to imines to produce pyridine bisimine NNN ligands; and Type 2, in which only one ketone group of 2,6-diacetylpyridine is condensed with an aniline derivative to give monoimine NNO coordination sets. Ligands of either type are coordinated to chromium(II) or chromium(III) chlorides, and activation of the resultant complexes with methylaluminoxane (MAO) produces highly active ethylene oligomerization and polymerization catalysts. Catalysts of Type 1 (NNN set) generally produce 1-butene when only two ortho alkyl substituents are present but switch to making waxes or polyethylene when the size and/or number of ortho substituents are increased. Catalysts of Type 2 (NNO set) produce waxes and polyethylene under all of the substitution patterns studied. The butene-producing catalysts can make 1-butene with 99.5+% purity, and the wax-producing catalysts make highly linear to moderately branched waxes, depending on the presence of an alpha-olefin comonomer.