Proton Relay in Iron Porphyrins for Hydrogen Evolution Reaction

The efficiency of the hydrogen evolution reaction (HER) can be facilitated by the presence of proton-transfer groups in the vicinity of the catalyst. A systematic investigation of the nature of the proton-transfer groups present and their interplay with bulk proton sources is warranted. The HERs electrocatalyzed by a series of iron porphyrins that vary in the nature and number of pendant amine groups are investigated using proton sources whose pK_a values vary from ∼9 to 15 in acetonitrile. Electrochemical data indicate that a simple iron porphyrin (FeTPP) can catalyze the HER at this Fe^I state where the rate-determining step is the intermolecular protonation of a Fe^III-H^- species produced upon protonation of the iron(I) porphyrin and does not need to be reduced to its formal Fe⁰ state. A linear free-energy correlation of the observed rate with pK_a of the acid source used suggests that the rate of the HER becomes almost independent of pK_a of the external acid used in the presence of the protonated distal residues. Protonation to the Fe^III-H^- species during the HER changes from intermolecular in FeTPP to intramolecular in FeTPP derivatives with pendant basic groups. However, the inclusion of too many pendant groups leads to a decrease in HER activity because the higher proton binding affinity of these residues slows proton transfer for the HER. These results enrich the existing understanding of how second-sphere proton-transfer residues alter both the kinetics and thermodynamics of transition-metal-catalyzed HER.