Jiang Hongjie, Zhao Jing, Meng Qingyu, Zhao Xiao-Kun, Guo Min, Hu Han-Shi, Li Jun, Chen Ning
College of Chemistry, Chemical Engineering and Materials Science and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, China.
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen, China.
Nat Chem. 2025 Jun 19. doi: 10.1038/s41557-025-01856-2.
Metal-ligand multiple bonds are ubiquitous in coordination and organometallic chemistry. In contrast, lanthanide-carbon multiple bonds are difficult to form. The isolation of complexes containing lanthanide-carbon double bonds with terminal methyl carbene (=CH) and lanthanide-carbon triple bonds remains challenging. Here we present the synthesis of a lanthanide-carbon triple bond contained inside an endohedral fullerene cage. More specifically, we report a cerium-carbide [Ce≡CSc] cluster encapsulated inside a C fullerene cage. The molecular structure of Ce≡CSc@C and the nature of the Ce≡C triple bond are studied through X-ray crystallography, spectroscopic analyses and quantum chemical calculations. Our data reveal a very short Ce≡C distance of 1.969(7) Å. Chemical bonding analysis suggests that the formation of the Ce≡C bond primarily arises from the stronger bonding affinity between carbon and cerium compared with scandium inside the encapsulated cluster. The fullerene cage plays a crucial role in stabilizing and protecting this trimetallic carbide cluster featuring a Ce≡C triple bond.
金属-配体多重键在配位化学和有机金属化学中普遍存在。相比之下，镧系元素-碳多重键难以形成。分离含有末端甲基卡宾（=CH）的镧系元素-碳双键和镧系元素-碳三键的配合物仍然具有挑战性。在此，我们展示了一种内包富勒烯笼中所含镧系元素-碳三键的合成方法。更具体地说，我们报道了一种封装在C富勒烯笼中的碳化铈[Ce≡CSc]簇。通过X射线晶体学、光谱分析和量子化学计算研究了Ce≡CSc@C的分子结构和Ce≡C三键的性质。我们的数据揭示了Ce≡C键的键长非常短，为1.969(7) Å。化学键分析表明，Ce≡C键的形成主要源于与封装簇内的钪相比，碳与铈之间更强的键合亲和力。富勒烯笼在稳定和保护这个具有Ce≡C三键的三金属碳化物簇方面起着至关重要的作用。
