Cheng Xin, Li Zi-Yu, Mou Li-Hui, Liu Qing-Yu, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Phys Chem Chem Phys. 2022 Oct 19;24(40):24950-24958. doi: 10.1039/d2cp02248f.
The activation and transformation of molecular nitrogen (N) by metal hydride species has attracted widespread attention due to its critical role in nitrogen fixation. Herein, the reactions between tantalum deuteride cluster anions TaD and N were investigated experimentally and theoretically. An unprecedented reaction channel of the liberation of a single D atom was observed and much superior reactivity was identified for TaD. Theoretical investigations indicate that the releasing of D atoms benefits from the completely dissociative adsorption of N on the dinuclear metal centres. The extra D atoms in TaD compared to TaD are helpful to create sufficient electron density at the adsorption site and modify the symmetry of active orbitals to facilitate a further reduction of N. This comparative study provides a molecular-level insight to understand the high structure-modulating capability of the additional hydride ligands in polyhydride species in the adsorption and activation of nitrogen molecules.
