Reactivity of Iron Hydride Anions Fe₂H^- (n = 0-3) with Carbon Dioxide

The hydrogenation of CO₂ 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 CO₂ 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 Fe₂H^- (n = 0-3) anions with CO₂ were investigated using mass spectrometry and quantum chemical calculations. The experimental results showed that the reduction of CO₂ into CO dominates all of these reactions, whereas Fe₂H^- and Fe₂H₂^- can induce the hydrogenation of CO₂ effectively to give rise to products Fe(HCO₂)^- and HFe(HCO₂)^-, respectively. The mechanistic aspects and the reactivity of Fe₂H^- with an increased number of H atoms in CO₂ hydrogenation were rationalized by theoretical calculations.