A series of [O−N(H)X]TiCl3 complexes derived from (arylamino)methylene phenol are prepared. The molecular structures of the complexes are characterized by 1H NMR, 13C NMR, and X-ray analysis. Upon activation with modified methylaluminoxane (MMAO), the titanium complexes display high thermal stability and single-site like ethylene (co)polymerization behavior at the temperatures of up to 150 °C. 1-Octene and 1-octadencene prove suitable to be incorporated into polyethylene backbone at 110 °C and the highest activity of 1.89 × 106 g/mol(Ti)·h·atm can be achieved. The pendant group X has great influence on the catalytic behaviors of the complexes, and PPh2 proves to be the optimal group. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2495–2503
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