Chen Xiuting, Wan Songpeng, Wang Qian, Gong Yu
Key Laboratory of Thorium Energy, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Nat Commun. 2024 Aug 20;15(1):7130. doi: 10.1038/s41467-024-51167-2.
Actinide metallacyclic chemistry has been of interest due to its involvement in various chemical processes. However, fundamental understanding on the key species, actinide metallacyclic complexes, is limited to metallacyclopropenes whereas little is known about the actinide metallacyclopropynes presumably due to their unusual high reactivity. Herein, we report the preparation of a thorium metallacyclopropyne complex (η-C ≡ C)ThCl in the gas phase by using electrospray ionization mass spectrometry, and it is generated via a single-ligand strategy through sequential losses of CO and HCl from the monopropynoate precursor (HC ≡ CCO)ThCl upon collision-induced dissociation. Alternatively, the dual-ligand strategy involving consecutive losses of two CO and one CH from the dipropynoate precursor (HC ≡ CCO)ThCl works as well. According to the reactivity experiments and theoretical calculations, (η-C ≡ C)ThCl possesses a dianionic ligand C coordinated to the Th(IV) center in a side-on fashion. Further bonding analysis demonstrates the presence of a triple bond between the two C atoms, and the Th 5 f orbitals are significantly involved in the Th-(C ≡ C) bonding. A Th metallacyclopropyne structure is thus established for (η-C ≡ C)ThCl.
锕系金属环化学因其参与各种化学过程而备受关注。然而，对于关键物种——锕系金属环配合物的基本认识仅限于金属环丙烯，而对于锕系金属环丙炔，由于其异常高的反应活性，人们所知甚少。在此，我们报道了通过电喷雾电离质谱法在气相中制备钍金属环丙炔配合物(η-C≡C)ThCl，它是通过单配体策略，在碰撞诱导解离时，由单丙炔酸酯前体(HC≡CCO)ThCl依次失去CO和HCl而产生的。或者，涉及从二丙炔酸酯前体(HC≡CCO)ThCl连续失去两个CO和一个CH的双配体策略也可行。根据反应性实验和理论计算，(η-C≡C)ThCl具有一个以侧基方式与Th(IV)中心配位的双阴离子配体C。进一步的键合分析表明两个C原子之间存在三键，并且Th 5f轨道显著参与了Th-(C≡C)键合。因此，为(η-C≡C)ThCl建立了一个钍金属环丙炔结构。
