A series of titanium complexes (CpTiCl)-Ti-*(OCHRCH2NAr) (CP* = C5Me5, R = H, Ar = phenyl (2a); R = H, Ar = 2,6-dimethylphenyl (2b); R = Me, Ar = phenyl (2c); R = Me, At = 2,6-dimethylphenyl (2d)) was prepared by the reaction of corresponding 2-phenylamino-ethanol derivatives with (CpTiCl3)-Ti-* in the presence of excessive triethylamine. All the titanium complexes display higher catalytic activity towards the syndiospecific polymerization of styrene in the presence of modified methylaluminoxane (MMAO) as a cocatalyst, yielding higher molecular weight polystyrenes with higher syndiotacticities and melting temperatures (T-m) than their mother complex (CpTiCl3)-Ti-*. When 2-(2,6-diisopropyl-phenylamino)-ethanol was reacted with (CpTiCl3)-Ti-*, an unexpected monodentate complex (CpTiCl2)-Ti-*((OCH2CH2NHC6H3Pr2)-Pr-i-2,6) 3 was obtained. The complex 3 displays relative low catalytic activity towards styrene polymerization, but produces higher molecular weight polystyrene with higher syndiotacticities. (c) 2005 Elsevier B.V. All rights reserved.