Synthetic Iron-Sulfur Clusters

Iron-sulfur clusters are essential cofactors for life and are ubiquitous in most enzymatic systems where they participate in electron transfer chains, coupled-proton electron transfers or directly catalyze complex transformations. Based on the design and synthesis of new iron-sulfur clusters, we aim to provide functional models for these transformations.

We have in particular demonstrated that synthetic Fe₄S₄ clusters can act as concerted proton electron transfer (CPET) mediators for electrocatalytic generation of metal hydride species, in analogy with the mechanisms observed in the Fe-Fe hydrogenase enzyme and exploited this feature in the context of CO₂ reduction to formic acid. Further exploring bio-inspired strategies for electron transfers and storage, we reported the preparation of the first complete redox series of Fe₄S₄ complexes that covers all accessible oxidation states, including the elusive all-ferrous oxidation state. Replicating the modulation of electric fields observed in gating enzymatic mechanism, we demonstrated that Fe₄S₄(SR)₄ models can exhibit dynamic redox potentials on-demand.