The sequential activation of H2 and N2 mediated by the gas-phase Sc3N+ clusters: Formation of amido unit.

The activation and hydrogenation of nitrogen are central in industry and in nature. Through a combination of mass spectrometry and quantum chemical calculations, this work reports an interesting result that scandium nitride cations Sc₃N⁺ can activate sequentially H₂ and N₂, and an amido unit (NH₂) is formed based on density functional theory calculations, which is one of the inevitable intermediates in the N₂ reduction reactions. If the activation step is reversed, i.e., sequential activation of first N₂ and then H₂, the reactivity decreases dramatically. An association mechanism, prevalent in some homogeneous catalysis and enzymatic mechanisms, is adopted in these gas-phase H₂ and N₂ activation reactions mediated by Sc₃N⁺ cations. The mechanistic insights are important to understand the mechanism of the conversion of H₂ and N₂ to NH₃ synthesis under ambient conditions. [ABSTRACT FROM AUTHOR]