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USc2C2 and USc2NC Clusters with U–C Triple Bond Character Stabilized Inside Fullerene Cages
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-17 , DOI: 10.1021/jacs.2c10231
Hongjie Jiang 1 , Xiaojuan Yu 2 , Min Guo 1 , Yang-Rong Yao 1 , Qingyu Meng 1 , Luis Echegoyen 3 , Jochen Autschbach 2 , Ning Chen 1
Affiliation  

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 C═U(VI)═C and C═U(V)═N 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.

中文翻译:

具有稳定在富勒烯笼内的 U-C 三键特征的 USc2C2 和 USc2NC 簇

与成熟的 d 区过渡金属卡宾配合物相比,f 区金属-碳多重键的化学性质尚不发达。在此,我们报道了两种新的锕系稀土混合金属碳化物和碳化氮簇富勒烯,USc 2 C 2 @ D 5h (6)-C 80和 USc 2 NC@ D 5h (6)-C 80,它们含有 U– C键具有三键特征,已成功合成并通过质谱、紫外-可见-近红外光谱、傅里叶变换红外光谱、单晶X射线衍射和DFT计算进行表征。晶体学研究表明,两个先前未报道的簇USc 2 C 2和USc 2 NC在D 5h (6)-C 80碳笼中稳定,并采用独特的三叶构型,其中C 2 /NC单元几乎垂直插入进入由 U 和两个 Sc 原子定义的平面。结合实验和理论研究进一步揭示了USc 2 C 2和USc 2 NC的键合结构,其中包含C=U(VI)=C和C=U(V)=N键合基序。两种化合物的电子结构确定为 U 6+ (Sc 2 ) 6+ (C 4– ) 2 @ D 5h (6)-C 80 4–和 U 5+ (Sc 2 ) 6+ (N) 3 – (C) 4– @ D 5h (6)-C 80 4–,分别。量子化学研究证实,两个分子中的 U-C 键显示出前所未有的多中心三键特征。这种独特的 U-C 多重键的发现让人们对铀化学的基础知识有了更深入的了解。
更新日期:2023-02-17
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