Hydrogen evolution driven by heteroatoms of bidentate N-heterocyclic ligands in iron(II) complexes

While Pt is considered the best catalyst for the electrocatalytic hydrogen evolution reaction (HER), it is evident that non-noble metal alternatives must be explored. In this regard, it is well known that the binding sites for non-noble metals play a pivotal role in facilitating efficient catalysis. Herein, we studied Fe(II) complexes with bidentate 2-(2'-pyridyl)benzoxazole (LO), 2-(2'-pyridyl)benzthiazole (LS), 2-(2'-pyridyl)benzimidazole (LNH), and 2-2'-bipyridyl (Lpy) ligands - by adding trifluoroacetic acid (TFA) to their acetonitrile solution - in order to examine how their reactivity towards protons under reductive conditions could be impacted by the non-coordinating heteroatoms (S, O, N, or none). By applying this ligand series, we found that the reduction potentials relevant for HER correlate with ligand basicity in the presence of TFA. Moreover, DFT calculations underlined the importance of charge distribution in the ligand-based LUMO and LUMO+1 orbitals of the complexes, dependent on the heterocycle. Kinetic studies and controlled potential electrolysis - using TFA as a proton source - revealed HER activities for the complexes with LNH, LO, and LS of k_obs = 0.03, 1.1, and 10.8 s^-1 at overpotentials of 0.81, 0.76, and 0.79 V, respectively, and pointed towards a correlation between the kinetics of the reaction and the non-coordinating heteroatoms of the ligands. In particular, the activity was associated with the [Fe(LS/O/NH)₂(S)₂]²⁺ form (S = solvent or substrate molecule), and the rate-determining step involved the formation of [Fe(H-H)]⁺, during the weakening of Fe-H and CF₃CO₂-H bonds, according to the experimental and DFT results.