A series of heteroligated (salicylaldiminato)(beta-enaminoketonato) titanium complexes [3-(t)Bu-2-OC(6)H(3)CH N(C(6)F(5))] [PhN=C(CF(3))CHCRO]TiCl(2) [3a: R Ph, 3b: R C(6)H(4)Cl(p), 3c: R = C(6)H(4)OMe(p), 3d: R = C(6)H(4)Me(p), 3e: R = C(6)H(4)Me(o)] were synthesized and characterized. Molecular structures of 3b and 3c were further confirmed by X-ray crystallographic analyses. In the presence of modified methylaluminoxane as a cocatalyst, these unsymmetric catalysts displayed favorable ability to incorporate 5-vinyl-2-norbornene (VNB) and 5-ethylidene-2-norbornene (ENB) into the polymer chains, affording high-molecular weight copolymers with high-comonomer incorporations and alternating sequence under the mild conditions. The comonomer concentration in the polymerization medium had a profound influence on the molecular weight distribution of the resultant copolymer. At initial comonomer concentration of higher than 0.4 mol/L, the titanium complexes with electron-donating groups in the beta-enaminoketonato moiety mediated room-temperature living ethylene/VNB or ENB copolymerizations. Polymerization results coupled with density functional theory calculations suggested that the highly controlled living copolymerization is probably a consequence of the difficulty in chain transfer of VNB (or ENB)-last-inserted species and some characteristics of living ethylene polymerization under limited conditions. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4626-4638, 2011