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

Autor: Yao YR; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China., Zhao J; Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China., Meng Q; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China., Hu HS; Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China., Guo M; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China., Yan Y; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China., Zhuang J; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China., Yang S; 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., Fortier S; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States., Echegoyen L; Institut Catalá d'Investigació Química, Ave. Països Catalans 16, 43007 Tarragona, Spain.; Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, United States., Schwarz WHE; Department 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., Li J; Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of the Ministry of Education, Tsinghua University, Beijing 100084, China.; Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China., Chen N; College of Chemistry, Chemical Engineering and Materials Science & State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou 215123, China.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2023 Nov 22; Vol. 145 (46), pp. 25440-25449. Date of Electronic Publication: 2023 Nov 13.
DOI: 10.1021/jacs.3c10042
Abstrakt: 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 C 72 and C 78 . The molecular structures of UCCe@C 2 n 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 2 n 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.
Databáze: MEDLINE