USc2C2 and USc2NC Clusters with U-C Triple Bond Character Stabilized Inside Fullerene Cages.
J Am Chem Soc
; 145(10): 5645-5654, 2023 Mar 15.
Article
em En
| MEDLINE
| ID: mdl-36800216
ABSTRACT
The chemistry of f-block metal-carbon multiple bonds is underdeveloped compared to well-established carbene complexes of the d-block transition metals. Herein, we report two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, which contain U-C bonds with triple bond character and were successfully synthesized and characterized by mass spectrometry, UV-vis-NIR spectroscopy, Fourier transform infrared spectroscopy, single crystal X-ray diffraction, and DFT calculations. Crystallographic studies show that the two previously unreported clusters, USc2C2 and USc2NC, are stabilized in the D5h(6)-C80 carbon cage and adopt unique trifoliate configurations, in which C2/NC units are almost vertically inserted into the plane defined by the U and two Sc atoms. Combined experimental and theoretical studies further reveal the bonding structure of USc2C2 and USc2NC, which contain CâU(VI)âC and CâU(V)âN bonding motifs. The electronic structures of the two compounds are determined as U6+(Sc2)6+(C4-)2@D5h(6)-C804- and U5+(Sc2)6+(N)3-(C)4-@D5h(6)-C804-, respectively. Quantum-chemical studies confirm that the U-C bonds in both molecules show unprecedented multicenter triple-bond character. The discovery of this unique U-C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Clinical_trials
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2023
Tipo de documento:
Article