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Complexes of titanium(IV) with bulky phenolic ligands such as 2-tert-butyl-4 methylphenol, 2, 4-di-tert-butyl phenol and 3,5-di-tert-butyl phenol were prepared and characterized. These catalyst precursors, formulated as [Ti(OPh * ) n (OPr i ) 4−n ] (OPh * = substituted phenol), were found to be active in polymerization of ethylene at higher temperatures in combination with ethylaluminum sesquichloride (Et 3 Al 2 Cl 3 ) as co-catalyst. It was observed that the reaction temperature and ethylene pressure had a pronounced effect on polymerization and the molecular weight of polyethylene obtained. In addition, this catalytic system predominantly produced linear, crystalline ultra-lowmolecular-weight polyethylenes narrow dispersities. The polyethylene waxes obtained with this catalytic system exhibit unique properties that have potential applications in surface coating and adhesive formulations.

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