| Abstract: | Main‐group complexes are shown to be viable electrocatalysts for the H2‐evolution reaction (HER) from acid. A series of antimony porphyrins with varying axial ligands were synthesized for electrocatalysis applications. The proton‐reduction catalytic properties of TPSb(OH)2 (TP=5,10,15,20‐tetra(p ‐tolyl)porphyrin) with two axial hydroxy ligands were studied in detail, demonstrating catalytic H2 production. Experiments, in conjunction with quantum chemistry calculations, show that the catalytic cycle is driven via the redox activity of both the porphyrin ligand and the Sb center. This study brings insight into main group catalysis and the role of redox‐active ligands during catalysis. |
