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Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b10247· OSTI ID:1596909
 [1];  [2];  [2];  [3];  [4];  [4];  [4];  [4];  [4];  [4];  [4];  [4];  [3];  [2];  [4]
  1. Soochow Univ. (China); University at Buffalo
  2. State Univ. of New York (SUNY), Buffalo, NY (United States)
  3. Univ. of Texas at El Paso, TX (United States)
  4. Soochow Univ. (China)
+ Show Author Affiliations
>Novel actinide cluster fullerenes, U2C2@Ih(7)-C80 and U2C2@D3h(5)-C78, were synthesized and fully characterized by mass spectrometry, single-crystal X-ray crystallography, UV–vis–NIR, nuclear magnetic resonance spectroscopy (NMR), X-ray absorption spectroscopy (XAS), Raman spectroscopy, IR spectroscopy, as well as density functional and multireference wave function calculations. The encapsulated U2C2 is a novel example of a uranium carbide cluster featuring two U centers bridged by a C≡C unit. The U–C bond distances in these U2C2 clusters are in the range between 2.130 and 2.421 Å. While the U2C2 cluster in U2C2@C80 adopts a butterfly-shaped geometry with a U–C2–U dihedral angle of 112.7° and a U–U distance of 3.855 Å, the U–U distance in U2C2@C78 is 4.164 Å and the resulting U–C2–U dihedral angle is increased to 149.1°. The combined experimental and quantum-chemical results suggest that the formal U oxidation state is +4 in the U2C2 cluster, and each U center transfers three electrons to the C2n cage and one electron to C2. Different from the strong U ＝ C covalent bonding reported for U2C2@ C80, the U–C bonds in U2C2 are less covalent and predominantly ionic. The C–C triple bond is somewhat weaker than in HCCH, and the C–C π bonds undergo donation bonding with the U centers. This work shows that the combination of the unique encapsulation effect of fullerene cages and the variable oxidation states of actinide elements can lead to the stabilization of novel actinide clusters, which are not accessible by conventional synthetic methods.
Research Organization:
Florida State Univ., Tallahassee, FL (United States)
Sponsoring Organization:
National Natural Science Foundation China (NNSFC); Robert A. Welch Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001136; SC0016568
OSTI ID:
1596909
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 51 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
chemical bonding
cluster
endohedral fullerenes
uranium carbide