Skip to main content
eScholarship
Open Access Publications from the University of California

A diuranium carbide cluster stabilized inside a C80 fullerene cage.

  • Author(s): Zhang, Xingxing
  • Li, Wanlu
  • Feng, Lai
  • Chen, Xin
  • Hansen, Andreas
  • Grimme, Stefan
  • Fortier, Skye
  • Sergentu, Dumitru-Claudiu
  • Duignan, Thomas J
  • Autschbach, Jochen
  • Wang, Shuao
  • Wang, Yaofeng
  • Velkos, Giorgios
  • Popov, Alexey A
  • Aghdassi, Nabi
  • Duhm, Steffen
  • Li, Xiaohong
  • Li, Jun
  • Echegoyen, Luis
  • Schwarz, WH Eugen
  • Chen, Ning
  • et al.
Abstract

Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing Ih(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

Main Content
Current View