The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States
Name
Angew Chem Int Ed - 2022 - Kim - The Elusive Mononitrosylated Fe4S4 Cluster in Three Redox States.pdf
Description
Published version
Size
2.12 MB
Format
Adobe PDF
Checksum (MD5)
25e79e8f36c8b6ba20745d74a4ac0b3d
Author(s)
Kim, Youngsuk
Sridharan, Arun
Suess, Daniel LM
Date Issued
2022
Journal
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
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivs License
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DOI of Published Version
https://doi.org/10.1002/ANIE.202213032
