The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States
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 re...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Wiley
2023
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| Online Access: | https://hdl.handle.net/1721.1/148038 |
| _version_ | 1811080557987102720 |
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| author | Kim, Youngsuk Sridharan, Arun Suess, Daniel LM |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Kim, Youngsuk Sridharan, Arun Suess, Daniel LM |
| author_sort | Kim, Youngsuk |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T11:33:29Z |
| format | Article |
| id | mit-1721.1/148038 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:33:29Z |
| publishDate | 2023 |
| publisher | Wiley |
| record_format | dspace |
| spelling | mit-1721.1/1480382023-02-15T03:30:24Z The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States Kim, Youngsuk Sridharan, Arun Suess, Daniel LM Massachusetts Institute of Technology. Department of Chemistry 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. 2023-02-14T15:05:58Z 2023-02-14T15:05:58Z 2022 2023-02-14T15:00:25Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/148038 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). en 10.1002/ANIE.202213032 Angewandte Chemie - International Edition Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Wiley Wiley |
| spellingShingle | Kim, Youngsuk Sridharan, Arun Suess, Daniel LM The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title | The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title_full | The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title_fullStr | The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title_full_unstemmed | The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title_short | The Elusive Mononitrosylated [Fe 4 S 4 ] Cluster in Three Redox States |
| title_sort | elusive mononitrosylated fe 4 s 4 cluster in three redox states |
| url | https://hdl.handle.net/1721.1/148038 |
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