Macrocycles containing 1, 1′-ferrocenyldiselenolato ligands on group 4 metallocenes

Abstract

Macrocyclic [Fe(η5-C5H4Se)2M(η5-C5H4R)2]2 [M = Ti (1), Zr (2), Hf (3), R = H; and M = Zr (4), Hf (5), R = tBu] were prepared and characterized by 77Se NMR spectroscopy and the crystal structures of 1–3 and 5 were determined by single-crystal X-ray diffraction. The crystal structure of 4 is known and the complex is isomorphous with 5. 1–5 form mutually similar macrocyclic tetranuclear complexes in which the alternating Fe(C5H4Se)2 and M(C5H4R)2 centers are linked by selenium bridges. The thermogravimetric analysis (TGA) of 1–3 under a helium atmosphere indicated that the complexes undergo a two-step decomposition upon heating. The final products were identified using powder X-ray diffraction as FexMSe2, indicating their potential as single-source precursors for functional materials.