Molecular Octa-Uranium Rings with Alternating Nitride and Azide Bridges

Uranium nitrides offer potential as future nuclear fuels and as probes of metal ligand multiple bonding involving the f-block actinide metals. However, few molecular examples are available for study owing to the difficulties in synthesis. Recent advances in organoactinide chemistry have provided a route to uranium nitride complexes that expands the options for developing UN chemistry. Several 24-membered uranium nitrogen rings, (UNUN₃)₄, have been synthesized by reduction of sodium azide with organometallic metallocene derivatives, [(C₅Me₄R)₂U][([micro]-Ph)₂BPh₂] (R = Me, H; Me = methyl, Ph = phenyl). The nanometer-sized rings contain unusual UNU nitride linkages that have short U-N distances within the double-bond range.