The effect of an electrical bias on the mechanism of decomposition of transients with metal-carbon σ bonds

When CCl₃CO₂^- reacts thermally with porous iron electrodes, the radical CCl₂CO₂^- is formed. This radical reacts with the surface of the electrode to form a transient with a Fe-C σ bond, Fe0^&_(S)-CCl ₂COO^-. The mechanism of decomposition of this transient depends on the electrical bias applied to the electrode: at a low bias of E > -0.9 V vs. SCE, HCCl₂COO^- is the major final product, whereas at a higher bias of E < -1.2 V vs. SCE, HC(O)CO₂ ^- is the major product.