The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States
Author(s)
Kim, Youngsuk; Sridharan, Arun; Suess, Daniel LM
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Iron-sulfur clusters are well-established targets in biological nitric oxide (NO) chemistry, but the key intermediate in these processes-a mononitrosylated [Fe4 S4 ] cluster-has not been fully characterized in a protein or a synthetic model thereof. Here, we report the synthesis of a three-member redox series of isostructural mononitrosylated [Fe4 S4 ] clusters. Mononitrosylation was achieved by binding NO to a 3 : 1 site-differentiated [Fe4 S4 ]+ cluster; subsequent oxidation and reduction afforded the other members of the series. All three clusters feature a local high-spin Fe3+ center antiferromagnetically coupled to 3 [NO]- . The observation of an anionic NO ligand suggests that NO binding is accompanied by formal electron transfer from the cluster to NO. Preliminary reactivity studies with the monocationic cluster demonstrate that exposure to excess NO degrades the cluster, supporting the intermediacy of mononitrosylated intermediates in NO sensing/signaling.
Date issued
2022Department
Massachusetts Institute of Technology. Department of ChemistryJournal
Angewandte Chemie - International Edition
Publisher
Wiley
Citation
Kim, Youngsuk, Sridharan, Arun and Suess, Daniel LM. 2022. "The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States." Angewandte Chemie - International Edition, 61 (47).
Version: Final published version