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]2ThNR
(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.