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.

Isopropoxy- and tert-butoxy-tris(dithiocarbamato)titanium(IV) complexes of five dithiocarbamate ligands were prepared and characterized by LDI-MS, (1)H NMR, (13)C NMR, and elemental analysis, as well as by crystallographic determination of two examples. Both showed strongly pi-coordinated alkoxy groups and two separate dithiocarbamate coordination environments that, in solution, were in rapid exchange. Cyclic voltammetry in CH(2)Cl(2) revealed irreversible but reproducible oxidation peaks between +1.2 and +1.6 V vs Ag/AgCl, about 1 V positive of those from the free ligands, as well as reduction peaks in the -1.9 to -2.2 V range vs Ag/AgCl assigned to Ti(IV/III) couples, and second reductions in some cases. The corresponding diisopropoxy-bis(dithiocarbamato) analogues were not isolable and slowly transformed to the more stable tris species. Indeed, these were shown to be in slow equilibrium.

With the goal of preparing Ti(IV) complexes bearing a sulfur-based redox function of possible use in electrocatalytic oxidations of alcohols at electrode surfaces, a series of seven 2,2'-dithiodianiline Schiff-base derivatives, including two new variations, were tested in reactions with Ti(OR)(4) (R = (i)Pr, (t)Bu). Instead of the expected dimetallic products of general formula [LTi(OR)(2)](2), mononuclear species LTi(OR)(2) were obtained, confirmed by crystallographic determinations to have an unprecedented, symmetrical, and macrocyclic arrangement with four-point binding to the metal center and with the disulfide moieties remaining uncoordinated. Cyclic voltammetry performed in CH(2)Cl(2) displayed oxidations at potentials useful for fuel cells (+1.1-1.5 V vs Ag/AgCl), but despite the uncoordinated disulfide moieties, the complexes were reticent to engage in reduction processes.