Synthesis, Structure, and Reactivity of a Thorium Metallocene Containing a 2,2′-Bipyridyl Ligand

Abstract

The reduction of [η5-1,2,4-(Me3C)3C5H2]2ThCl2 (1) with potassium graphite in the presence of 2,2′-bipyridine gives the purple thorium bipy metallocene [η5-1,2,4-(Me3C)3C5H2]2Th(bipy) (2) in good yield. Complex 2 has been characterized by various spectroscopic techniques, elemental analysis, and single-crystal X-ray diffraction. Complex 2 is a good synthon for low-valent thorium, as shown by the reactivity with silver halides, trityl chloride, pyridine-N-oxide, RN3, 9-diazofluorene, and diphenyl diselenide, yielding the halide metallocenes [η5-1,2,4-(Me3C)3C5H2]2ThX2 (X = Cl (1), F (3), Br (4)), oxo metallocene [η5-1,2,4-(Me3C)3C5H2]2ThO(py) (5), imido metallocenes [η5-1,2,4-(Me3C)3C5H2]2Th═NR (R = p-tolyl (6), Ph3C (7), Me3Si (8), (9-C13H8)═N (9)), and selenido complex [η5-1,2,4-(Me3C)3C5H2]Th(SePh)3(bipy) (10a), in quantitative conversions.