A diuranium carbide cluster stabilized inside a C80 fullerene cage

Xingxing Zhang, Wanlu Li, Lai Feng, Xin Chen, Andreas Hansen, Stefan Grimme, Skye Fortier, Dumitru-Claudiu Sergentu, Thomas J. Duignan, Jochen Autschbach, Shuao Wang, Yaofeng Wang, Giorgios Velkos, Alexey A. Popov, Nabi Aghdassi, Steffen Duhm, Xiaohong Li, Jun Li (), Luis Echegoyen (), W. H. Eugen Schwarz and Ning Chen ()
Additional contact information
Xingxing Zhang: Soochow University
Wanlu Li: Tsinghua University
Lai Feng: Soochow University
Xin Chen: Tsinghua University
Andreas Hansen: Universität Bonn
Stefan Grimme: Universität Bonn
Skye Fortier: University of Texas at El Paso
Dumitru-Claudiu Sergentu: University at Buffalo, State University of New York
Thomas J. Duignan: University at Buffalo, State University of New York
Jochen Autschbach: University at Buffalo, State University of New York
Shuao Wang: Soochow University
Yaofeng Wang: Soochow University
Giorgios Velkos: Nanoscale Chemistry, Leibniz Institute for Solid State and Materials Research
Alexey A. Popov: Nanoscale Chemistry, Leibniz Institute for Solid State and Materials Research
Nabi Aghdassi: Soochow University
Steffen Duhm: Soochow University
Xiaohong Li: Soochow University
Jun Li: Tsinghua University
Luis Echegoyen: Universität Bonn
W. H. Eugen Schwarz: Tsinghua University
Ning Chen: Soochow University

Nature Communications, 2018, vol. 9, issue 1, 1-8

Abstract: 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.

Date: 2018
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DOI: 10.1038/s41467-018-05210-8

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