A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates
Although alkyl complexes of [Fe₄S₄] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein repor...
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2019
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| Online Access: | https://hdl.handle.net/1721.1/122277 |
| _version_ | 1811077703504232448 |
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| author | Ye, Mengshan Thompson, Niklas B. Brown, Alexandra C. Suess, Daniel L. M. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Ye, Mengshan Thompson, Niklas B. Brown, Alexandra C. Suess, Daniel L. M. |
| author_sort | Ye, Mengshan |
| collection | MIT |
| description | Although alkyl complexes of [Fe₄S₄] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein report the synthesis and characterization of a 3:1 site-differentiated [Fe₄S₄]²⁺-alkyl cluster. Whereas [Fe₄S₄]²⁺ clusters typically exhibit pairwise delocalized electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer spectroscopic and computational studies suggest that the highly electron-releasing alkyl group partially localizes the charge distribution within the cubane, an effect that has not been previously observed in tetrahedrally coordinated [Fe₄S₄] clusters. |
| first_indexed | 2024-09-23T10:47:14Z |
| format | Article |
| id | mit-1721.1/122277 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T10:47:14Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1222772022-09-27T15:01:44Z A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates Ye, Mengshan Thompson, Niklas B. Brown, Alexandra C. Suess, Daniel L. M. Massachusetts Institute of Technology. Department of Chemistry Although alkyl complexes of [Fe₄S₄] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein report the synthesis and characterization of a 3:1 site-differentiated [Fe₄S₄]²⁺-alkyl cluster. Whereas [Fe₄S₄]²⁺ clusters typically exhibit pairwise delocalized electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer spectroscopic and computational studies suggest that the highly electron-releasing alkyl group partially localizes the charge distribution within the cubane, an effect that has not been previously observed in tetrahedrally coordinated [Fe₄S₄] clusters. 2019-09-23T18:18:36Z 2019-09-23T18:18:36Z 2019-08 2019-07 2019-09-20T14:12:16Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/122277 Ye, Mengshan et al. "A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates." Journal of the American Chemical Society 141, 34 (August 2019): 13330-13335 © 2019 American Chemical Society en http://dx.doi.org/10.1021/jacs.9b06975 Journal of the American Chemical Society Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Ye, Mengshan Thompson, Niklas B. Brown, Alexandra C. Suess, Daniel L. M. A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title | A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title_full | A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title_fullStr | A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title_full_unstemmed | A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title_short | A Synthetic Model of Enzymatic [Fe₄S₄]–Alkyl Intermediates |
| title_sort | synthetic model of enzymatic fe₄s₄ alkyl intermediates |
| url | https://hdl.handle.net/1721.1/122277 |
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