The synthesis and characterization of three complexes of the type (N-(3-tert-butylsalicylidene)-R)2TiCl2 [R=2,6-difluorophenyl 1, R=2,6-dimethylphenyl 2, R=phenyl 3] is reported and compared with the highly active R=2,3,4,5,6,–pentafluorophenyl 4. The complexes were tested for ethylene polymerization when activated with different co-catalysts, giving high catalytic activity when activated with methylaluminoxane for complexes 3 and 4. Complex 3 is the only catalyst to be inactive when activated with diethylaluminum chloride. Unexpectedly, for complexes 1 and 2, no catalytic activity is recorded when butylated hydroxytoluene in methylaluminoxane is used to remove the trimethylaluminum, while the catalytic activity for complex 3 is retained. NMR study on the activation of the four complexes in the presence of common alkyl aluminum co-catalysts suggests the formation of Ti(III) species in the presence of tri-iso-butylaluminum, and also the formation of NR−CH2 (R: −Al(CH2CH(CH3)2)2) bond from the N=C−H bond of the ligand explaining the absence of catalytic activity. Density functional theory calculations using B3LYP and a combination of basis sets (6-31+G and cc-pVTZ) were performed on the catalyst precursors and the activated species showing insights into the frontier orbitals, localizing the LUMO on the imino bond elucidating their reactivity. Mulliken charges are also reported and an unexpected relationship between the nitrogen on the ligands and the molecular weight is observed.