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Zhang et al 2018, A diuranium carbide cluster stabilized.pdf985.5 kBAdobe PDFView/Open
Title: A diuranium carbide cluster stabilized inside a C80 fullerene cage
Authors: Zhang, X.Li, W.Feng, L.Chen, X.Hansen, A.Grimme, S.Fortier, S.Sergentu, D.-C.Duignan, T.J.Autschbach, J.Wang, S.Wang, Y.Velkos, G.Popov, A.A.Aghdassi, N.Duhm, S.Li, X.Li, J.Echegoyen, L.Schwarz, W.H.E.Chen, N.
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Issue Date: 2018
Published in: Nature Communications Vol. 9 (2018), No. 1
Publisher: London : Nature Publishing Group
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 I h(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I h(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@I h(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@I h(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.
Keywords: carbon; diuranium carbide; fullerene; unclassified drug; uranium; actinide; chemical bonding; chemistry; detection method; fullerene; inorganic compound; ligand; oxidation; stabilization; Article; carbon nuclear magnetic resonance; covalent bond; crystal structure; electrochemical analysis; high temperature; low temperature; molecular stability; oxidation; oxidation reduction potential; photoelectron spectroscopy; photoluminescence; quantum chemistry; synthesis; theoretical study; X ray diffraction
DDC: 530
License: CC BY 4.0 Unported
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