Annuaire
Seminar: Victor MOUGEL
| Quand ? |
06/11/2025 à 10:30 |
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| Où ? |
Salle Collet |
| Contact |
Olivier Maury |
Abstract: Iron-sulfur (FeS) cubane-type clusters are among the most abundant and functionally versatile metallocofactors encountered in the biosphere. Their central role stems from their unique electronic properties, characterized by an exceedingly dense manifold of low-lying excited states, as well as their rich electron-transfer (ET) chemistry. Recently, we reported the synthesis of a complete redox series of [Fe4S4(SAr)4]n‑ complexes (n = 0-4),(1), demonstrating their direct relevance to biomimetic ET reactivity, particularly conformationally gated ETs.(2) This has enabled us to decipher the biophysical basis for this unique ET mechanism, ultimately being controlled by the local electrostatic environment of the cofactor. These insights into redox modulation and electronic structure laid the foundation for the rational design of larger iron-sulfur assemblies. Leveraging our detailed knowledge of the (electro-)chemical properties of [Fe4S4(SAr)4]n‑ complexes, we will present the stepwise construction of synthetic K-cluster mimics, which may provide a molecular-level perspective on the earliest stages of FeMo-cofactor maturation in NifB.(3)
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1) L. Grunwald, M. Clémancey, D. Klose, L. Dubois, S. Gambarelli, G. Jeschke, M. Wörle, G. Blondin, V. Mougel A complete biomimetic iron-sulfur cubane redox series PNAS, 2022, 119 (31), e2122677119 |
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2) L. Grunwald, M. Inoue, P. Cendoya Carril, M. Wörle, V. Mougel Gated electron transfers at synthetic iron-sulfur cubanes Chem, 2024, 10(1), 365-387. |
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3) L. Grunwald,M. L. Weber, H. Seng ,M. Clemancey ,H. Wang ,M. Wörle ,Y. Yoda ,S. P. Cramer ,G. Blondin, V. Mougel Stepwise and Reversible Assembly of 2Fe–2S Rhombs to 8Fe–8S Clusters and Their Topological Interconversions Nat. Chem. 2025,17, 1586–1595 |
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