<i>N</i>‑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