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

Abstract

Abstract The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C−H bond. Herein, we report that HCO 2 − and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH − . The FeH − anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum‐chemical calculations. Gas‐phase HCO 2 − was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas‐phase study parallels similar behavior of a condensed‐phase iron catalyst.