Synthesis, Characterization, and Sol-Gel Behavior of Dichlorotitanium(IV) (O-Alkyl, O-Cycloalkyl, and O-Aryl Trithiophosphates)

Dichlorotitanium(IV) trithiophosphates of the type TiCl2[(RO)P(S)S2] (where R = Me, Et, Prn, Pri, Bun, Bus, Bui, Ami, Ph and cyclohexyl) have been synthesized for the first time by the reaction of titanium tetrachloride with potassium trithiophosphates in a 1:1 molar ratio in anhydrous benzene. Sol-gel chemistry of these titanium(IV) compounds has been studied in dry benzene by treatment with hydrogen sulfide gas. These newly synthesized derivatives have been characterized by elemental analysis (C, H, S, Cl, and Ti), molecular weight measurement, and spectral [IR and multinuclear NMR (1H, 13C, and 31P)] studies. The bonding mode of trithiophosphate ligands and tentative structure around titanium(IV) are discussed.