Electrification of a Milstein-type catalyst for alcohol reformation.

Novel energy and atom efficiency processes will be keys to develop the sustainable chemical industry of the future. Electrification could play an important role, by allowing to fine-tune energy input and using the ideal redox agent: the electron. Here we demonstrate that a commercially available Milstein ruthenium catalyst (1) can be used to promote the electrochemical oxidation of ethanol to ethyl acetate and acetate, thus demonstrating the four electron oxidation under preparative conditions. Cyclic voltammetry and DFT-calculations are used to devise a possible catalytic cycle based on a thermal chemical step generating the key hydride intermediate. Successful electrification of Milstein-type catalysts opens a pathway to use alcohols as a renewable feedstock for the generation of esters and other key building blocks in organic chemistry, thus contributing to increase energy efficiency in organic redox chemistry.

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

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 CO2 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 CO2, 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 CO2; these are discussed in terms of key intermediates such as iron hydrides or Fe-CO2 adducts, where the ligand coordination motif, together with the presence of co-additives such as Brønsted acids, nucleophiles, or CO2 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 CO2 are finally given.