Work

Isolation of uranocenium, the bis-[8]annulene uranium cation

Year: 2026

Type: article

Abstract: Uranocene, [U IV (η 8 -C 8 H 8 ) 2 ], is the actinide equivalent to ferrocene. While ferrocene is readily oxidised to the ferrocenium cation, higher oxidation states of uranocene are unknown. Here we report the elusive uranocenium cation, [U V (η 8 -C 8 H 8 ) 2 ] + , and demonstrate using electron paramagnetic resonance spectroscopy and magnetometry that this formal U(V) complex has a 5 f 1 ground state. Enhanced uranium 5 f and 6 d mixing into filled δ-symmetry bonding orbitals in uranocenium, compared to uranocene, amplifies interorbital electron–electron repulsion, and counteracts bond length contraction, which minimises structural change. This manifests in solution where the uranocene/uranocenium redox couple exhibits near-ideal electrochemical reversibility, and in the solid-state where X-ray diffraction studies show minimal U–C bond length change upon oxidation. This demonstrates a case where actinide covalency governs molecular structure and physical properties across both solid and solution phases.

Source: Nature Communications

DOI: 10.1038/s41467-026-77066-2