Article Dans Une Revue Proceedings of the National Academy of Sciences of the United States of America Année : 2022

A complete biomimetic iron-sulfur cubane redox series

Résumé

Synthetic iron-sulfur cubanes are models for biological cofactors, which are essential to delineate oxidation states in the more complex enzymatic systems. However, a complete series of [Fe4S4](n) complexes spanning all redox states accessible by 1-electron transformations of the individual iron atoms (n = 0-4+) has never been prepared, deterring the methodical comparison of structure and spectroscopic signature. Here, we demonstrate that the use of a bulky arylthiolate ligand promoting the encapsulation of alkali-metal cations in the vicinity of the cubane enables the synthesis of such a series. Characterization by EPR, Fe-57 M_ossbauer spectroscopy, UV-visible electronic absorption, variabletemperature X-ray diffraction analysis, and cyclic voltammetry reveals key trends for the geometry of the Fe4S4 core as well as for the M_ossbauer isomer shift, which both correlate systematically with oxidation state. Furthermore, we confirm the S = 4 electronic ground state of the most reduced member of the series, [Fe4S4](0), and provide electrochemical evidence that it is accessible within 0.82 V from the [Fe4S4](2+) state, highlighting its relevance as a mimic of the nitrogenase iron protein cluster.

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hal-04032654 , version 1 (15-11-2024)

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Liam Grunwald, Martin Clémancey, Daniel Klose, Lionel Dubois, Serge Gambarelli, et al.. A complete biomimetic iron-sulfur cubane redox series. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119 (31), pp.e2122677119. ⟨10.1073/pnas.2122677119⟩. ⟨hal-04032654⟩
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