The synthesis and structural characterization of [Et 4N] 2[Ti(SPh) 6] and trimeric [Ti 3O(SPh) 3Cl 4(CH 3CN) 5]·CH 3CN·(C 2H 5) 2O complexes

Abstract

The reaction of TiCl 4 with 6 equiv. of NaSPh in the presence of organic cations such as Et 4N + or PPh 4 + proceeds to yield a novel homoleptic arylthiolate Ti(IV) complex, [Ti(SPh) 6] 2−. The Et 4N salt of [Ti(SPh) 6] 2− has been structurally determined. The coordination geometry around the metal ion is a regular octahedron in which the central titanium ion is located on the crystallographic inversion center. The infrared (IR) spectrum of compound I exhibits the characteristic Ti–S bond stretching vibrations of thiophenolate ligands at 480 and 430 cm −1, and the 1H NMR spectrum in CD 3CN displays characteristic Et 4N + resonance peaks and six thiophenolate resonance peaks which are consistent with the solid state structure. The reaction of TiCl 4 with 3 or 4 equiv. of NaSPh in CH 3CN yields the unexpected mixture of dark purple [TiCl 3(CH 3CN) 3] and dark red [Ti 3O(SPh) 3Cl 4(CH 3CN) 5]·CH 3CN·(C 2H 5) 2O ( II) complexes. Complex II has been structurally determined by single X-ray crystallography. The IR spectrum of complex II exhibits a μ 3–O stretching vibration at 600 cm −1 and Ti–S vibrations of the thiophenolate ligand at 481 and 429 cm −1.