A Thorium(IV) metallacyclopropyne complex

Xiuting Chen, Songpeng Wan, Qian Wang and Yu Gong ()
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Xiuting Chen: Chinese Academy of Sciences
Songpeng Wan: Chinese Academy of Sciences
Qian Wang: Chinese Academy of Sciences
Yu Gong: Chinese Academy of Sciences

Nature Communications, 2024, vol. 15, issue 1, 1-7

Abstract: Abstract 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 (η2-C ≡ C)ThCl3– in the gas phase by using electrospray ionization mass spectrometry, and it is generated via a single-ligand strategy through sequential losses of CO2 and HCl from the monopropynoate precursor (HC ≡ CCO2)ThCl4– upon collision-induced dissociation. Alternatively, the dual-ligand strategy involving consecutive losses of two CO2 and one C2H2 from the dipropynoate precursor (HC ≡ CCO2)2ThCl3– works as well. According to the reactivity experiments and theoretical calculations, (η2-C ≡ C)ThCl3– possesses a dianionic ligand C22– 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 (η2-C ≡ C)ThCl3–.

Date: 2024
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DOI: 10.1038/s41467-024-51167-2

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