| Autor: |
Li, Yao, Mou, Li-Hui, Jiang, Gui-Duo, Li, Zi-Yu, He, Sheng-Gui, Chen, Hui |
| Zdroj: |
Inorganic Chemistry; June 2024, Vol. 63 Issue: 23 p10775-10785, 11p |
| Abstrakt: |
Gas-phase metal clusters are ideal models to explore transition-metal-mediated N2activation mechanism. However, the effective design and search of reactive clusters in N2activation are currently hindered by the lack of clear guidelines. Inspired by the Sabatier principle, we discovered in this work that N2initial adsorption energy (ΔEads) is an important parameter to control the N2activation reactivity of metal clusters in the gas phase. This mechanistic insight obtained from high-level calculations rationalizes the N2activation reactivity of many previously reported metal clusters when combined with the known factor determining the N≡N cleavage process. Furthermore, based on this guideline of ΔEads, we successfully designed several new reactive clusters for cleaving N≡N triple bond under mild conditions, including FeV2S2–, TaV2C2–, and TaV2C3–, the high N2activation reactivity of which has been fully corroborated in our gas phase experiments employing mass spectrometry with collision-induced dissociation. The importance of ΔEadsrevealed in this work not only reshapes our understanding of N2activation reactions in the gas phase but also could have implication for other N2activation processes in the condensed phase. The more general establishment of this new perspective on N2activation reactivity warrants future experimental and computational studies. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
|
