Titanocene complexes of the N-methyl and N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolates and 4,5-diselenolate ligands

Cp2Ti(dithiolene) and Cp2Ti(diselenolene) complexes containing the N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Me-thiazdt), the N-phenyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (Ph-thiazdt) and the N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (Me-thiazds) have been synthesized. Three approaches have been developed in order to generate the dithiolene or the diselenolene ligands which were reacted with Cp2TiCl2 to form the corresponding heteroleptic complexes. Their X-ray crystal structures, UV–Vis absorption spectra as well as their redox properties, determined by cyclic voltammetry have been investigated and discussed. Variable-temperature 1H NMR experiments have been performed in order to determine the activation energies of the chelate ring inversion.

Graphical abstractCp2Ti(R-thiazdt) and Cp2Ti(R-thiazds) complexes were prepared following three synthetic approaches through the reaction of 1,3-thiazoline-2-thione-4,5-dithiolate (R-thiazdt) and -4,5- diselenolate ligand (R-thiazds) with Cp2TiCl2. The complexes were characterized and compared using X-ray structure determinations, cyclic voltammetry, UV–Vis spectroscopy, as well as variable-temperature 1H NMR experiments.Figure optionsDownload full-size imageDownload as PowerPoint slide