Liu Yun-Zhu, Li Xiao-Na, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2020 Oct 15;124(41):8414-8420. doi: 10.1021/acs.jpca.0c06986. Epub 2020 Sep 30.
The hydrogenation of CO into value-added complexes is of great importance for both environmental and economic issues. Metal hydrides are good models for the active sites to explore the nature of CO hydrogenation; however, the fundamental insights into C-H bond formation are still far from clear because of the complexity of real-life catalysts. Herein, gas-phase reactions of the FeH ( = 0-3) anions with CO were investigated using mass spectrometry and quantum chemical calculations. The experimental results showed that the reduction of CO into CO dominates all of these reactions, whereas FeH and FeH can induce the hydrogenation of CO effectively to give rise to products Fe(HCO) and HFe(HCO), respectively. The mechanistic aspects and the reactivity of FeH with an increased number of H atoms in CO hydrogenation were rationalized by theoretical calculations.
将一氧化碳氢化为增值配合物对于环境和经济问题都非常重要。金属氢化物是探索一氧化碳氢化本质的活性位点的良好模型；然而，由于实际催化剂的复杂性，对碳氢键形成的基本认识仍远不清楚。在此，使用质谱和量子化学计算研究了FeH（n = 0-3）阴离子与一氧化碳的气相反应。实验结果表明，将一氧化碳还原为一氧化碳主导了所有这些反应，而FeH和FeH可以分别有效地诱导一氧化碳的氢化，从而产生产物Fe（HCO）和HFe（HCO）。通过理论计算对一氧化碳氢化中氢原子数量增加时FeH的机理和反应活性进行了合理化解释。
