In‐Situ and Real‐time Monitoring of Mechanochemical Preparation of Li₂Mg(NH₂BH₃)₄ and Na₂Mg(NH₂BH₃)₄ and Their Thermal Dehydrogenation

Abstract

For the first time, in situ monitoring of uninterrupted mechanochemical synthesis of two bimetallic amidoboranes, M₂ Mg(NH₂ BH₃ )₄ (M=Li, Na), by means of Raman spectroscopy, has been applied. This approach allowed real-time observation of key intermediate phases, and a straightforward follow-up of the reaction course. Detailed analysis of time-dependent spectra revealed a two-step mechanism through MNH₂ BH₃ ⋅NH₃ BH₃ adducts as key intermediate phases which further reacted with MgH₂ , giving M₂ Mg(NH₂ BH₃ )₄ as final products. The intermediates partially take a competitive pathway toward the oligomeric M(BH₃ NH₂ BH₂ NH₂ BH₃ ) phases. The crystal structure of the novel bimetallic amidoborane Li₂ Mg(NH₂ BH₃ )₄ was solved from high-resolution powder diffraction data and showed an analogous metal coordination to Na₂ Mg(NH₂ BH₃ )₄ , but a significantly different crystal packing. Li₂ Mg(NH₂ BH₃ )₄ thermally dehydrogenates releasing highly pure H₂ in the amount of 7 wt.%, and at a lower temperature then its sodium analogue, making it significantly more viable for practical applications.