Ligand Protonation at Carbon, not Nitrogen, during H₂ Production with Amine-Rich Iron Electrocatalysts

We present monometallic H₂ production electrocatalysts containing electron-rich triamine-cyclopentadienyl (Cp) ligands coordinated to iron. After selective CO extrusion from the iron tricarbonyl precursors, electrocatalysis is observed via cyclic voltammetry in the presence of an exogenous acid. Contrary to the fact that amines in the secondary coordination sphere are often protonated during electrocatalysis, comprehensive quantum-chemical calculations indicate that the amines likely do not function as proton relays; instead, endo-Cp ring protonation is most favorable after 1e^- reduction. This unusual mechanistic pathway emphasizes the need to consider a broad domain of H⁺/e^- addition products by synergistically combining experimental and theoretical resources.