N-Aryloxide-Amidinate Thorium Complexes

Hanhua Xu, Ze-Jie Lv, Xiao Chen, Zhenfeng Xi, Junnian Wei*

Inorg. Chem., 2024. DOI: 10.1021/acs.inorgchem.3c04505.

        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]Th^IVCp*(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 KC₈, the [ONNO]Th^IV-bipyridyl•̅ radical dimer complex (5) and [ONNO]Th^IV-bipyridyl^2– dianionic dimer species (6) were obtained, respectively.