N-Aryloxide-Amidinate Thorium Complexes.

ABSTRACT

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]ThIVCp*(LiCl)}2 (4) was obtained. In complex 2, the two ArO- arms bonded from the same ligand to different ThIV 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]ThIV-bipyridyl•̅ radical dimer complex (5) and [ONNO]ThIV-bipyridyl2- dianionic dimer species (6) were obtained, respectively.