Formation of Gas‐Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions

Abstract

The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO2 and formation of a C−H bond. Herein, we report that HCO2− and CO can be formed in the thermal reaction of CO2 with a diatomic metal hydride species, FeH−. The FeH− anions were produced by laser ablation, and the reaction with CO2 was analyzed by mass spectrometry and quantum‐chemical calculations. Gas‐phase HCO2− was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO2 hydrogenation in this gas‐phase study parallels similar behavior of a condensed‐phase iron catalyst.

Reactivity of Cobalt Clusters Con±/0 with Ammonia: Co3+ Cluster Catalysis for NH3 Dehydrogenation

“…In seeking suitable catalysts to replace the precious metal, earth-abundant light transition metals have attracted reasonable attention because their 3d electrons are associated with novel catalytic activity for a few important reactions, − such as NO x decomposition, CO 2 capture, − and water/ammonia dissociation. − For example, gas-phase reactions of size-selected cationic Fe n + clusters with ammonia have been studied, , and the reactivity of Fe 4 + was illustrated for the catalytic dehydrogenation of NH 3 . Also, early studies have demonstrated the adsorptive reactions of ammonia with neutral Co n and Ni n clusters .…”