Synthesis, structure, and reactivity of a thorium metallocene containing a 2,2-bipyridyl ligand

Article abstract of DOI:10.1021/om201015f

The reduction of [⁵-1,2,4-(Me₃C)C₅H _2]2ThCl2 (1) with potassium graphite in the presence of 2,2-bipyridine gives the purple thorium bipy metallocene [ ⁵-1,2,4- (Me₃C)C₅H_2]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 [ ⁵-1,2,4-(Me₃C) ₃C₅H_2]2ThX2 (X = Cl (1), F (3), Br (4)), oxo metallocene [ ⁵-1,2,4-(Me3C)3C5H2]2ThO(py) (5), imido metallocenes [ ⁵-1,2,4- (Me₃C) C₅H_2]2Th=NR (R = p-tolyl (6), Ph3C (7), Me3Si (8), (9-C13H8)=N (9)), and selenido complex [ ⁵-1,2,4- (Me3C)3C5H2]Th(SePh)3(bipy) (10a), in quantitative conversions.