Experimental and Theoretical Study of N₂ Adsorption on Hydrogenated Y₂C₄H⁻ and Dehydrogenated Y₂C₄⁻ Cluster Anions at Room Temperature

The adsorption of atmospheric dinitrogen (N₂) on transition metal sites is an important topic in chemistry, which is regarded as the prerequisite for the activation of robust N≡N bonds in biological and industrial fields. Metal hydride bonds play an important part in the adsorption of N₂, while the role of hydrogen has not been comprehensively studied. Herein, we report the N₂ adsorption on the well-defined Y₂C₄H_0,1⁻ cluster anions under mild conditions by using mass spectrometry and density functional theory calculations. The mass spectrometry results reveal that the reactivity of N₂ adsorption on Y₂C₄H⁻ is 50 times higher than that on Y₂C₄⁻ clusters. Further analysis reveals the important role of the H atom: (1) the presence of the H atom modifies the charge distribution of the Y₂C₄H⁻ anion; (2) the approach of N₂ to Y₂C₄H⁻ is more favorable kinetically compared to that to Y₂C₄⁻; and (3) a natural charge analysis shows that two Y atoms and one Y atom are the major electron donors in the Y₂C₄⁻ and Y₂C₄H⁻ anion clusters, respectively. This work provides new clues to the rational design of TM-based catalysts by efficiently doping hydrogen atoms to modulate the reactivity towards N₂.