Molecular Electrochemical Reduction of CO2 beyond Two Electrons

CO2 molecular electrochemical reduction has recently led to remarkable advancements. High performing catalysts have been prepared that mainly produce carbon monoxide (CO) and formic acid (HCOOH). Studies reporting highly reduced products (formed with more than two electrons) remain scarce, but the field is now quickly emerging. Driving such multi-electron, multi-proton catalytic reactions with molecular catalysts would offer unlimited possibilities for tuning and controlling catalytic active site configuration/environment. In this perspective, we discuss known examples and draw a first unified reactivity scheme. Starting with reports on C1 products such as formaldehyde, methanol, and methane, we then address the formation of C?C bonds and associated intricate pathways. Eventually, we provide critical insights to sharpen the interpretation and analysis of existing and upcoming reports.