USc2C2 and USc2NC Clusters with U–C Triple Bond Character Stabilized Inside Fullerene Cages

Jiang, Hongjie; Yu, Xiaojuan; Guo, Min; Yao, Yang-Rong; Meng, Qingyu; Echegoyen, Luis; Autschbach, Jochen; Chen, Ning

doi:10.1021/jacs.2c10231

USc₂C₂ and USc₂NC Clusters with U–C Triple Bond Character Stabilized Inside Fullerene Cages

Journal Article · Fri Feb 17 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c10231· OSTI ID:2479715

Jiang, Hongjie ^[1]; ^[2]; Guo, Min ^[1]; Yao, Yang-Rong ^[1]; Meng, Qingyu ^[1]; ^[3]; ^[2]; ^[1]

Soochow University, Jiangsu (China)
University at Buffalo, State University of New York, NY (United States)
University of Texas at El Paso, TX (United States)

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@D_5h(6)-C₈₀ and USc₂NC@D_5h(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 D_5h(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 C=U(VI)=C and C=U(V)=N bonding motifs. The electronic structures of the two compounds are determined as U⁶⁺(Sc₂)⁶⁺(C^4–)₂@D_5h(6)-C₈₀^4– and U⁵⁺(Sc₂)⁶⁺(N)^3–(C)^4–@D_5h(6)-C₈₀^4–, respectively. Quantum-chemical studies confirm that the U–C bonds in both molecules show unprecedented multicenter triple-bond character. Furthermore, the discovery of this unique U–C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.

View Accepted Manuscript (DOE)

Research Organization:: University at Buffalo, State University of New York, NY (United States)

Sponsoring Organization:: National Natural Science Foundation China; Natural Science Foundation of Jiangsu Province; Robert A Welch Foundation; US National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001136

OSTI ID:: 2479715

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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USc2C2 and USc2NC Clusters with U–C Triple Bond Character Stabilized Inside Fullerene Cages

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