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 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.