Carbon Dioxide Reduction Mediated by Iron Catalysts: Mechanism and Intermediates That Guide Selectivity

[Image: see text] The reduction of carbon dioxide represents an ambitious target, with potential impact on several of the United Nations’ sustainable development goals including climate action, renewable energy, sustainable cities, and communities. This process shares a common issue with other redox reactions involved in energy-related schemes (i.e., proton reduction to hydrogen and water oxidation to oxygen), that is, the need for a catalyst in order to proceed at sustainable rates. Moreover, the reduction of CO(2) faces an additional selectivity complication, since several products can be formed, including carbon monoxide, formic acid/formate, methanol, and methane. In this Mini-Review, we will discuss iron-based molecular catalysts that catalyze the reduction of CO(2), focusing in particular on the selectivity of the processes, which is rationalized and guided on the basis of the reaction mechanism. Inspired by the active sites of carbon monoxide dehydrogenases, several synthetic systems have been proposed for the reduction of CO(2); these are discussed in terms of key intermediates such as iron hydrides or Fe-CO(2) adducts, where the ligand coordination motif, together with the presence of co-additives such as Brønsted acids, nucleophiles, or CO(2) trapping moieties, can guide the selectivity of the reaction. A mechanistic comparison is traced with heterogeneous iron single-atom catalysts. Perspectives on the use of molecular catalysts in devices for sustainable reduction of CO(2) are finally given.