Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)(2)(NMe2)(2) (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C6H4-4-Me; 3e: R = C6H4-4-t-Bu; 3f. R = C6H3-3,5-Me-2) and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)(2)(NMe2)(2) (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe2)(4) with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe2)(4) (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPY)(4)(THF)-T-. (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-arylpyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C6H3-3,5-Me-2)-SPy](2)(NMe2)(2) (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 degrees C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes. (c) 2006 Elsevier Ltd. All rights reserved.