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

Macrocyclic [Fe(η 5 -C 5 H 4 Se) 2 M(η 5 -C 5 H 4 R) 2 ] 2 [M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ), R = H; and M = Zr ( 4 ), Hf ( 5 ), R = t Bu] were prepared and characterized by 77 Se 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(C 5 H 4 Se) 2 and M(C 5 H 4 R) 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 Fe x MSe 2 , indicating their potential as single-source precursors for functional materials. Macrocyclic [Fe(η 5 -C 5 H 4 Se) 2 M(η 5 -C 5 H 4 R) 2 ] 2 [M = Ti ( 1 ), Zr ( 2 ), Hf ( 3 ), R = H; and M = Zr ( 4 ), Hf ( 5 ), R = t Bu] were prepared and characterized by 77 Se NMR spectroscopy and the crystal structures of 1-3 and 5 were determined by single-crystal X-ray diffraction.