Biomimetic models of uniquely ligated iron-sulfur (Fe-S) clusters are of interest due to the more recent discovery of mitoNEET, a protein associated with type 2 diabetes that contains a [2Fe-2S] cluster ligated by three cysteines and one histidine. The exact function of mitoNEET remains unclear, but studies have suggested the unique ligation gives rise to Fe-S cluster transfer. In this talk we will discuss our synthetic approach that uses one equivalent of trifluoroacetic acid (TFA) to singly substitute an all thiolate bound [2Fe-2S] model cluster, (NEt4)[Fe2S2(SPh)4], at -60°C. 19F NMR spectroscopy (-60°C) reveals broadening of the TFA signal when bound to the [2Fe-2S] cluster. Peak splitting of the phenyl thiolate protons observed by 1H NMR (-60°C) spectroscopy is consistent with breaking symmetry of an all thiolate bound cluster, along with evolution of one equivalent of thiol suggests a singly substituted [2Fe-2S] cluster. Upon warming to room temperature, this TFA bound species converts to [4Fe-4S] cluster and produces one equivalent of disulfide while releasing anionic TFA. This cluster conversion without addition of an external reductant serves as a synthetic model for how nature uses [2Fe-2S] clusters as building blocks for cubane type [4Fe-4S] clusters, and a potential function for mitoNEET.

Acid induced iron-sulfur (Fe-S) cluster conversion via single substituted intermediate

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.