Xtreme Labs News​​​​ – 2025

 

Abstract:
For the activation of nitrogen and its reduction to ammonia, transition metals are crucial in biological as well as industrial processes. So far, only a few binary transition metal compounds with nitrogen dimer anions are known, whereas a ternary compound has remained undiscovered as yet. Here, we report on the synthesis and properties of the first ternary transition metal compound, namely, BeW10N14(N2), which exhibits dinitrogen anions. It was synthesized in a high-temperature high-pressure approach from W2Be4N5. The crystal structure, elucidated with synchrotron radiation, unites WN7 capped trigonal prisms with intriguing BeN6 octahedra and (N2)-anions. Elastic and electronic properties of the title compound were corroborated by DFT calculations, revealing simultaneous ultra-incompressible and metallic behavior. The synthesis and investigation of the first ternary transition metal nitride with dinitrogen units opens the door to a new field of research on nitride and pernitride chemistry.


https://onlinelibrary.wiley.com/doi/full/10.1002/ange.202505778

 

Description unavailableAbstract:
Reacting praseodymium(IV) oxide with oxygen at 27 GPa in a diamond anvil cell yielded the oxide peroxide Pr2IV(O2)O3, which was characterized by single crystal X-ray diffraction on multi-grain samples, Raman spectroscopy and quantum theoretical calculations at various pressure points. The presence of tetravalent praseodymium ions is supported by electronic structure calculations, showing a band gap of ca. 1.2 eV, which is consistent with the anticipated chemical model of an ionic solid. Pr2(O2)O3 thus far represents the most oxygen rich phase of any binary compound of a lanthanoid and oxygen and is the first example of a peroxide anion next to Pr4+. Additionally, these results demonstrate that instead of oxidizing the praseodymium ions past their +IV oxidation state, oxygen undergoes a comproportionation to form peroxide anions. Direct oxidation of the oxide anions by Pr4+-ions was ruled out by a control experiment in argon instead of oxygen, where no oxidation of oxide ions was observed.


https://onlinelibrary.wiley.com/doi/full/10.1002/anie.202422929