Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer
Two non-heme iron–nitrosyl species, [Fe₂(N-Et-HPTB)(O₂CPh)(NO)₂](BF4)₂(1a) and [Fe₂(N-Et-HPTB)(DMF)₂(NO)(OH)](BF₄)₃ (2a), are characterized by FTIR and resonance Raman spectroscopy. Binding of NO is reversible in both complexes, which are prone to NO photolysis under visible light illumination. Phot...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2017
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| Online Access: | http://hdl.handle.net/1721.1/110422 |
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| author | Jiang, Yunbo Hayashi, Takahiro Matsumura, Hirotoshi Do, Loi H. Majumdar, Amit Lippard, Stephen J. Moënne-Loccoz, Pierre |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Jiang, Yunbo Hayashi, Takahiro Matsumura, Hirotoshi Do, Loi H. Majumdar, Amit Lippard, Stephen J. Moënne-Loccoz, Pierre |
| author_sort | Jiang, Yunbo |
| collection | MIT |
| description | Two non-heme iron–nitrosyl species, [Fe₂(N-Et-HPTB)(O₂CPh)(NO)₂](BF4)₂(1a) and [Fe₂(N-Et-HPTB)(DMF)₂(NO)(OH)](BF₄)₃ (2a), are characterized by FTIR and resonance Raman spectroscopy. Binding of NO is reversible in both complexes, which are prone to NO photolysis under visible light illumination. Photoproduction of N₂O occurs in high yield for 1a but not 2a. Low-temperature FTIR photolysis experiments with 1a in acetonitrile do not reveal any intermediate species, but in THF at room temperature, a new {FeNO}⁷ species quickly forms under illumination and exhibits a ν(NO) vibration indicative of nitroxyl-like character. This metastable species reacts further under illumination to produce N₂O. A reaction mechanism is proposed, and implications for NO reduction in flavodiiron proteins are discussed. |
| first_indexed | 2024-09-23T13:10:06Z |
| format | Article |
| id | mit-1721.1/110422 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:10:06Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1104222024-06-28T14:46:22Z Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer Jiang, Yunbo Hayashi, Takahiro Matsumura, Hirotoshi Do, Loi H. Majumdar, Amit Lippard, Stephen J. Moënne-Loccoz, Pierre Massachusetts Institute of Technology. Department of Chemistry Two non-heme iron–nitrosyl species, [Fe₂(N-Et-HPTB)(O₂CPh)(NO)₂](BF4)₂(1a) and [Fe₂(N-Et-HPTB)(DMF)₂(NO)(OH)](BF₄)₃ (2a), are characterized by FTIR and resonance Raman spectroscopy. Binding of NO is reversible in both complexes, which are prone to NO photolysis under visible light illumination. Photoproduction of N₂O occurs in high yield for 1a but not 2a. Low-temperature FTIR photolysis experiments with 1a in acetonitrile do not reveal any intermediate species, but in THF at room temperature, a new {FeNO}⁷ species quickly forms under illumination and exhibits a ν(NO) vibration indicative of nitroxyl-like character. This metastable species reacts further under illumination to produce N₂O. A reaction mechanism is proposed, and implications for NO reduction in flavodiiron proteins are discussed. National Institutes of Health (U.S.) (GM074785) National Institutes of Health (U.S.) (GM032134) 2017-07-03T15:26:58Z 2017-07-03T15:26:58Z 2014-08 2014-05 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/110422 Jiang, Yunbo; Hayashi, Takahiro; Matsumura, Hirotoshi; Do, Loi H.; Majumdar, Amit; Lippard, Stephen J. and Moënne-Loccoz, Pierre. “ Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer.” Journal of the American Chemical Society 136, 36 (September 2014): 12524–12527 © 2014 American Chemical Society en_US http://dx.doi.org/10.1021/ja504343t Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Jiang, Yunbo Hayashi, Takahiro Matsumura, Hirotoshi Do, Loi H. Majumdar, Amit Lippard, Stephen J. Moënne-Loccoz, Pierre Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title | Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title_full | Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title_fullStr | Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title_full_unstemmed | Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title_short | Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer |
| title_sort | light induced n₂o production from a non heme iron nitrosyl dimer |
| url | http://hdl.handle.net/1721.1/110422 |
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