The Chemistry of Some Organosulphur Titanium (IV) Compounds

Chapter I of this thesis is a review of the chemistry of titanium (IV) with thiols and dithiols.
Chapter II consists of a review of the preparation and reactions of tetrabenzyl titanium.
Chapter III comprises a discussion of the complexes of titanium (IV) with a variety of thiols and dithiols which have been prepared and characterised during the course of this investigation. Some reactions of tetrabenzyl-titanium with thiols and dithiols are also discussed.
The reaction of dithiol with titanium tetraisopropoxide led to the formation of the disubstituted product in the case of the 1,2-dithiols but no products were isolated from the reactions with 1,3- and 1,4- dithiols. Bis(toluene-3,4-dithiolato)titanium (IV) was the only fully substituted compound obtained using titanium tetraisopropoxide as the starting material.
A series of Lewis base adducts of the dithiolato complexes were prepared. For the complexes with bidentate Lewis bases two methods of preparation were used. One method involved direct reaction of the Lewis base with the dithiolato complex; the other method consisted of mixing solutions of titanium tetraisopropoxide, the dithiol and the Lewis base in the appropriate proportions.
Proton n.m.r., far infrared and molecular weight data are reported for the dithiolato complexes and their Lewis base adducts. The adducts were found to be monomeric in solution and it is postulated that the compounds with bidentate Lewis bases adopt the cis-structure.
An attempt to form the triethylamine adduct of bis(isopropoxy) toluene-3 ,4-dithiolatotitanium (IV) led to the formation of a tris (dithiolato) complex containing the triethylammonium cation. The reaction was repeated using diethylamine and the corresponding triscomplex containing the diethylammonium cation was obtained. Far infrared and u.v.-visible spectral data are reported for these complexes.
The reaction of tetrabenzyltitanium with aliphatic dithiols gave the fully substituted bis(dithiolato) complexes. The reaction of tetrabenzyltitanium with monothiols gave products which could not be identified.
The interaction of titanium tetraisopropoxide with o-aminobenzenthiol led to the formation of the disubstituted product. It is concluded from the spectroscopic data that the complex is a six-coordinate species with two coordinating -NH2 groups.