Synthetic and structural studies have been performed for two thiolate complexes of titanium(IV). The reaction between Ti(NEt2)4 and 10 equivalents of C6F5SH at room temperature resulted in the formation of the ionic complex [Et2NH2]3[Ti(SC6F5)5][SC6F5]2. The related reaction between Ti(NEt2)4 and 4 equivalents of C6F5SH at room temperature, in the presence of a two electron donor ligand L (2,6-dimethylpyridine or tetrahydrothiophene), resulted in the isolation of the ionic complex [Et2NH2][Ti(SC6F5)4(NEt2)]. However, if the reaction between Ti(NEt2)4 and 4 equivalents of C6F5SH is carried out without the addition of L, the first compound is formed rather than the second. The two new complexes have been characterised by X-ray crystallography. [Et2NH2]3[Ti(SC6F5)5][SC6F5]2 is the first structurally characterised example of a five-co-ordinate homoleptic sulfur-bonded titanium complex. Both adopt similar sheet structures held together by π–π and C–F⋯π interactions.
