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

• Published in: Journal of organometallic chemistry 2008-08, Vol.693 (16), p.2755-2760
• Main Authors: Eid, Samar, Roisnel, Thierry, Lorcy, Dominique
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Crystal structure; Diselenolene; Dithiolene; Organic chemistry; Thiazole; Titanocene
• ISSN: 0022-328X; 1872-8561; 0022-328X
• DOI: 10.1016/j.jorganchem.2008.05.021

Cp 2Ti(R-thiazdt) and Cp 2Ti(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 Cp 2TiCl 2. The complexes were characterized and compared using X-ray structure determinations, cyclic voltammetry, UV–Vis spectroscopy, as well as variable-temperature 1H NMR experiments. Cp 2Ti(dithiolene) and Cp 2Ti(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 Cp 2TiCl 2 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.