Chemical transformation of dithiolene ligands in heteroleptic and homoleptic complexes (M = Ti, Zn, Au)

Heteroleptic and homoleptic dithiolene metal complexes such as Cp2Ti(dithiolene), [Zn(dithiolene)2]2− and [Au(dithiolene)2]−1 complexes have been synthesized from the 1-tertiobutyl-1,3-thiazoline-2-thione-4,5-dithiolate (tBu-thiazdt) dithiolene ligand. The reactivity of these complexes towards iodomethane (MeI) has been examined. Both the titanocene and the gold complexes undergo a transformation of the tBu-1,3-thiazoline-2-thione core to a 2-methylthio-1,3-thiazole one with elimination of the tBu substituent. The reaction of MeI with the Zn complex leads to a tris(thiomethyl)-thiazole derivative due to the alkylation of the sulfur atoms and the decoordination together with the transformation into the thiazole core. Electrochemical, spectral and X-ray diffraction investigations carried out on these various complexes are also presented.