N-Aryloxide-Amidinate Thorium Complexes

An N-aryloxide-amidine ligand (1), [ONNO] ligand, integrating phenoxide (PhO-) and amidine ligands through methylene linkers, was employed in actinide chemistry. Upon reaction of the deprotonated ligand with ThCl4(DME)(2) in ether, the corresponding dimer complex 2 was obtained. Upon treatment of 2 with KCp* (Cp* = Cp(Me)(5)) in tetrahydrofuran, the corresponding {[ONNO](ThCp)-Cp-IV*(LiCl)}(2) (4) was obtained. In complex 2, the two ArO- arms bonded from the same ligand to different Th-IV centers. In contrast, both ArO- arms coordinated to the same metal center in 4. Notably, when a mixture of 2 and bipyridine was treated with one or two equiv of KC8, the [ONNO]Th-IV-bipyridyl center dot radical dimer complex (5) and [ONNO]Th-IV-bipyridyl(2-) dianionic dimer species (6) were obtained, respectively.