Dithiocarbamate complexes of Ti(IV) alkoxides: synthesis, characterization, and electrochemistry.
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.
Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario, Canada M3J 1P3.
Alberto
A
Donzelli
Pierre G
PG
Potvin