Bioinspired Diiron Complex with Proton Shuttling and Redox-Active Ligand for Electrocatalytic Hydrogen Evolution

A μ-oxo diiron complex, featuring the pyridine-2,6-dicarboxamide-based thiazoline-derived redox-active ligand, H₂L (H₂L = N²,N⁶-bis(4,5-dihydrothiazol-2-yl)pyridine-2,6-dicarboxamide), was synthesized and thoroughly characterized. [Feμ-O)-Fe] showed electrocatalytic hydrogen evolution reaction activity in the presence of different organic acids of varying pK_a values in dimethylformamide. Through electrochemical analysis, we found that [Feμ-O)-Fe] is a precatalyst that undergoes concerted two-electron reduction to generate an active catalyst. Fourier transform infrared spectrum of reduced species and density functional theory (DFT) investigation indicate that the active catalyst contains a bridged hydroxo unit which serves as a local proton source for the Fe(III) hydride intermediate to release H₂. We propose that in this active catalyst, the thiazolinium moiety acts as a proton-transferring group. Additionally, under sufficiently strong acidic conditions, bridged oxygen gets protonated before two-electron reduction. In the presence of exogenous acids of varying strengths, it displays electro-assisted catalytic response at a distinct applied potential. Stepwise electron-transfer and protonation reactions on the metal center and the ligand were studied through DFT to understand the thermodynamically favorable pathways. An ECEC or EECC mechanism is proposed depending on the acid strength and applied potential.