Experimental and Theoretical Study of N Adsorption on Hydrogenated YCH and Dehydrogenated YC Cluster Anions at Room Temperature.

The adsorption of atmospheric dinitrogen (N) 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 N, while the role of hydrogen has not been comprehensively studied. Herein, we report the N adsorption on the well-defined YCH cluster anions under mild conditions by using mass spectrometry and density functional theory calculations. The mass spectrometry results reveal that the reactivity of N adsorption on YCH is 50 times higher than that on YC clusters. Further analysis reveals the important role of the H atom: (1) the presence of the H atom modifies the charge distribution of the YCH anion; (2) the approach of N to YCH is more favorable kinetically compared to that to YC; and (3) a natural charge analysis shows that two Y atoms and one Y atom are the major electron donors in the YC and YCH 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 N.