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

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.