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.