Synthesis and Characterization of U≡C Triple Bonds in Fullerene Compounds
Yang-Rong Yao1, Jing Zhao2, Qingyu Meng1, Han-Shi Hu2, Min Guo1, Yingjing Yan1, Jiaxin Zhuang1, Shangfeng Yang3, Skye Fortier4, Luis Echegoyen5, W. H. Eugen Schwarz6, Jun Li2,7*（李隽）, and Ning Chen1*（谌宁）
1College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China
2Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China;
3Department of Materials Science and Engineering, CAS Key Laboratory of Materials for Energy
Conversion, Anhui Laboratory of Advanced Photon Science and Technology, University of Science and Technology of China, Hefei 230026, China
4Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States
5Institut Catalá d′Investigació Química, 43007 Tarragona, Spain; Department of Chemistry and
Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States
6Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China; Physikalische und Theoretische Chemie, Universität Siegen, Siegen 57068, Germany
7Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China
J. Am. Chem. Soc. 2023, 145, 25440−25449
Abstract：Despite decades of efforts, the actinide−carbon triple bond has remained an elusive target, defying synthesis in any isolable compound. Herein, we report the successful synthesis of uranium−carbon triple bonds in carbide-bridged bimetallic [U≡C–Ce] units encapsulated inside the fullerene cages of C72 and C78. The molecular structures of UCCe@C2n and the nature of the U≡C triple bond were characterized through X-ray crystallography and various spectroscopic analyses, revealing very short uranium−carbon bonds of 1.921(6) and 1.930(6) Å, with the metals existing in their highest oxidation states of +6 and +4 for uranium and cerium, respectively. Quantum-chemical studies further demonstrate that the C2n cages are crucial for stabilizing the [UVI≡C–CeIV] units through covalent and coordinative interactions. This work offers a new fundamental understanding of the elusive uranium−carbon triple bond and informs the design of complexes with similar bonding motifs, opening up new possibilities for creating distinctive molecular compounds and materials.
链接：//pubs.acs.org/doi/10.1021/jacs.3c10042
