| Photochemistry of the Dinitrosyl Iron Complex [S5Fe(NO)2]- Leading to Reversible Formation of [S5Fe(μ-S)2FeS5]2-: Spectroscopic Characterization of Species Relevant to the Nitric Oxide Modification and Repair of [2Fe−2S] Ferredoxins | |
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| 學年 | 93 |
| 學期 | 1 |
| 出版（發表）日期 | 2004-08-01 |
| 作品名稱 | Photochemistry of the Dinitrosyl Iron Complex [S5Fe(NO)2]- Leading to Reversible Formation of [S5Fe(μ-S)2FeS5]2-: Spectroscopic Characterization of Species Relevant to the Nitric Oxide Modification and Repair of [2Fe−2S] Ferredoxins |
| 作品名稱（其他語言） | |
| 著者 | Tsai, Ming-Li; Chen, Chiao-Chun; Hsu, I-Jui; Ke, Shyue-Chu; Hsieh, Chung-Hung; Chiang, Kuo-An; Lee, Gene-Hsiang; Wang, Yu; Chen, Jin-Ming; Lee, Jyh-Fu; Liaw, Wen-Feng |
| 單位 | 淡江大學化學學系 |
| 出版者 | Washington, DC: American Chemical Society |
| 著錄名稱、卷期、頁數 | Inorganic Chemistry 43(16), pp.5159-5167 |
| 摘要 | The reaction of [PPN][Fe(CO)3(NO)] and S8 in a 1:1 molar ratio in THF proceeded to give the dinitrosyl iron complex [PPN][S5Fe(NO)2] (1) and the known [PPN]2[S5Fe(μ-S)2FeS5] (2). EPR signals of g values gz = 2.0148, gx = 2.0270, and gy = 2.0485 at 77 K confirmed the existence of the unpaired electron in compound 1. The temperature-dependent magnetic moment of complex 1 indicates that the ground state is one unpaired electron with (St, SL) = (1/2, 1) at very low temperature (St is the total spin quantum number of the system; SL is the sum of the spin quantum numbers of two NO ligands). The O K-edge absorptions of complex 1 and [(NO)Fe(S2CNEt2)2] at 532.1 and 532.5 eV are assigned to the transition of 1s → π*(NO) and 1s → π*(NO+), respectively. For the electronic structure of the {Fe(NO)2} core, DFT calculations, magnetic susceptibility measurement, EPR, and Fe K-/L-edge XAS spectroscopy of complex 1 lead to a description of {Fe1+(•NO)2}9. [2Fe−2S] cluster 2 treated with nitric oxide in THF shows that cluster 2 is transformed into the dinitrosyl iron complex 1 identified by IR, UV−vis, and X-ray diffraction analysis. The reaction may be reversed by the photolysis of the THF solution of 1 in the presence of the NO-accepting reagent [(C4H8O)Fe(S,S-C6H4)2]- to reform 2. This result demonstrates a successful biomimetic reaction cycle of the degradation and reassembly of [2Fe−2S] cluster [S5Fe(μ-S)2FeS5]2- relevant to the repair of nitric oxide-modified [2Fe−2S] ferredoxin by cysteine desulfurase and l-cysteine in vitro. |
| 關鍵字 | |
| 語言 | en |
| ISSN | 0020-1669 1520-510X |
| 期刊性質 | 國外 |
| 收錄於 | |
| 產學合作 | |
| 通訊作者 | |
| 審稿制度 | 是 |
| 國別 | USA |
| 公開徵稿 | |
| 出版型式 | 紙本 電子版 |
| 相關連結 |
機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/97584 ) |
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