Synthesis and Characterization of U≡C Triple Bonds in Fullerene Compounds

Yang-Rong Yao; Jing Zhao; Qingyu Meng; Han-Shi Hu; Min Guo; Yingjing Yan; Jiaxin Zhuang; Shangfeng Yang; Skye Fortier; Luis Echegoyen; W H Eugen Schwarz; Jun Li; Ning Chen

doi:10.1021/jacs.3c10042

Synthesis and Characterization of U≡C Triple Bonds in Fullerene Compounds

J Am Chem Soc. 2023 Nov 22;145(46):25440-25449. doi: 10.1021/jacs.3c10042. Epub 2023 Nov 13.

Authors

Yang-Rong Yao¹, Jing Zhao², Qingyu Meng¹, Han-Shi Hu², Min Guo¹, Yingjing Yan¹, Jiaxin Zhuang¹, Shangfeng Yang³, Skye Fortier⁴, Luis Echegoyen^{5

4}, W H Eugen Schwarz^{2

6}, Jun Li^{2

7}, Ning Chen¹

Affiliations

¹ College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China.
² Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China.
³ Department 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.
⁴ Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States.
⁵ Institut Catalá d'Investigació Química, Ave. Països Catalans 16, 43007 Tarragona, Spain.
⁶ Physikalische und Theoretische Chemie, Universität Siegen, Siegen 57068, Germany.
⁷ Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.

PMID: 37955678
DOI: 10.1021/jacs.3c10042

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@C_2n 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 C_2n cages are crucial for stabilizing the [U^VI≡C-Ce^IV] 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.