Isolating the lanthanide in this oxidation state suggests a shift in some periodic tables

Isolating the lanthanide in this oxidation state suggests a shift in some periodic tables

Nature Chemistry - The most common oxidation state for lanthanide elements is +3, and, beyond cerium, examples of these elements exhibiting higher oxidation states remain scarce. Now, a molecular...

While several ligand systems support uranium across a range of oxidation states, spanning more than two oxidation states in a conserved coordination geometry is uncommon among structurally authenticated complexes. Imidophosphorane ligands significantly stabilize high-valent lanthanide and actinide complexes. Here, we report a series of homoleptic uranium imidophosphorane complexes, spanning the +4, +5 and +6 oxidation states in a four-coordinate pseudotetrahedral ligand field. The +6 oxidation state is accessible using a mild ferrocenium oxidant, yielding a rare example of U6+ in a pseudotetrahedral coordination environment. As the formal oxidation state increases, the U–N distances gradually contract, consistent with the Shannon ionic radii of U4+/5+/6+. Compared to reported complexes, the short U–N distances observed in the U6+ complex are more comparable to dianionic imido ligands than monoanionic amido ligands.