Isopropoxy- and tert-butoxy-(salicylideneamino-2-thiophenolato)titanium(IV) complexes from seven different salicylaldehydes were prepared and characterized. Two examples,diisopropoxy(4′-methoxysalicylideneamino-2-thiophenolato)titanium(IV) and di-tert-butoxy(salicylideneamino-2-thiophenolato)titanium(IV), were also characterized crystallographically. Three other examples crystallized as L2Ti species, one of which was an unusual dinuclear complex in which the ligands had dimerized through S–S interactions and formed amino linkages in an unexpected redox exchange. In all cases, cyclic voltammetry in CH2Cl2 showed irreversible oxidations at +1.2–1.4 V vs. Ag/AgCl. 2-Propanol induced a cathodic shift of the first oxidation potentials without apparent decomposition.