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]ThIV Cp*(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.