Synthesis and Isolation of Thorium Dinitrogen Complexes: 5f Orbital Matters

Xuechao Yan, Yuanjin Chen, Yixi Wang, Zhu-Bao Yin, Zhenfeng Xi, Junnian Wei*

Inorg. Chem. 2025. DOI: 10.1021/acs.inorgchem.5c03635.

        Thorium–dinitrogen complexes, long proposed as critical intermediates for actinide-mediated dinitrogen activation and bond cleavage, have not been isolated. In this work, three heterobimetallic [Cr]–N2–[Th] complexes featuring a Th–N2 moiety were synthesized via a metathesis reaction between a chromium(0) dinitrogen precursor and Th(IV) chloride derivatives. X-ray crystallographic analysis unambiguously confirmed their heterobimetallic [Cr]–N2–[Th] bridging geometry. Density functional theory (DFT) calculations revealed non-negligible 5f orbital contributions to the Th–N bonding interactions.