Electrochemical Formation C-S Bonds from CO2 and Small Molecule Sulfur Species

The formation of C-S bonds is an important step in the synthesis of pharmaceutical, biological, and chemical products. A very attractive green route to C-S bond containing species would be one driven through electrocatalysis using abundant small molecule precursors but examples within this context are largely absent from the literature. To this end, this work demonstrates the use of CO2 and SO32- as cheap building blocks that couple on the surface Cu-based heterogeneous catalysts to form hydroxymethanesulfonate, sulfoacetate and methane sulfonate for the first time, with Faradaic efficiencies of up to 9.5%. A combination of operando measurements and computational modelling reveal that *CHOH formed on metallic Cu is a key electrophilic intermediate that is nucleophilically attacked by SO32- in the principal C-S bond forming step. In all, the proof-of-concept for electrocatalytic C-S bond formation and mechanistic insights gained stand to substantially broaden the scope of the emerging field of electrosynthesis.