Metal and organometal complexes of oxy- and thio-phosphorus acids—I. O,O-Alkylene and dialkyl dithiophosphates of titanium(IV)

Abstract

O,O-Alkylene and dialkyl dithiophosphates of titanium(IV), Cl 4- n Ti(dtp) n [ n = 2, 3 and 4; dtp = S(S) POCMe 2CMe 2O or S(S)P(OEt) 2; n = 4 and dtp = S(S) POCHMeCHMeO , S(S) POCH 2CMe 2CH 2O and S(S)P(OPr i ) 2] have been synthesized by the reactions of titanium tetrachloride with ammonium or sodium salts of O,O-alkylene and dialkyl dithiophosphoric acids in appropriate stoichiometric ratios in refluxing benzene. All these complexes are hydrolysable, dark red semi-solids or viscous liquids and are soluble in common organic solvents when freshly prepared. Ionic tetrachlorodithiophosphatotitanate(IV) complexes, [M]+[TiCl 4(S 2 POCMe 2CMe 2O )] − (M = ammonium or pyridinium) have been obtained as insoluble yellow solids by mixing the reactants in equimolar ratios. All of these compounds have been characterized by elemental analyses, IR and NMR ( 1H, 13C and 31P) spectral studies. A few codisproportionation reactions of these dithiophosphato complexes have also been studied by 31P NMR spectroscopy.