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.

Transformation of the dithiolene ligand induced by methyl iodide within homoleptic and heteroleptic metal dithiolene complexes.Figure optionsDownload as PowerPoint slide