Bipyridyl thorium metallocenes [5-1,2,4-(Me3C)3C5H2]2Th(bipy) (1) and [5-1,3-(Me3C)2C5H3]2Th(bipy) (2) have been investigated by magnetic susceptibility and computational studies. The magnetic susceptibility data reveal that 1 and 2 are not diamagnetic, but they behave as temperature independent paramagnets (TIPs). To rationalize this observation, density functional theory (DFT) and complete active space SCF (CASSCF) calculations have been undertaken, which indicated that Cp2Th(bipy) has indeed a Th(IV)(bipy2-) ground state (f0d0 2, S = 0), but the open-shell singlet (f0d1 1, S = 0) (almost degenerate with its triplet congener) is lying only 9.2 kcal/mol higher in energy. Complexes 1 and 2 react cleanly with Ph2CS to give [ 5-1,2,4-(Me3C)3C5H2]2Th[(bipy)(SCPh2)] (3) and [ 5-1,3-(Me3C)2C5H3]2Th[(bipy)(SCPh2)] (4), respectively, in quantitative conversions. Since no intermediates were observed experimentally, this reaction was also studied computationally.
Coordinationof Ph2CS to 2 in its S = 0 ground state is not possible, but Ph2CS can coordinate to 2 in its triplet state (S = 1) upon which a single electron transfer (SET) from the (bipy2-) fragment to Ph2CS followed by C-C coupling takes place.