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 ThCl 4 (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]Th IV Cp*-(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 KC 8 , the [ONNO]Th IV -bipyridyl• ̅ radical dimer complex (5) and [ONNO]Th IV -bipyridyl 2− dianionic dimer species (6) were obtained, respectively.