| Oxygen Binding to Sulfur in Nitrosylated Iron−Thiolate Complexes: Relevance to the Fe-Containing Nitrile Hydratases | |
|---|---|
| 學年 | 92 |
| 學期 | 1 |
| 出版（發表）日期 | 2003-09-01 |
| 作品名稱 | Oxygen Binding to Sulfur in Nitrosylated Iron−Thiolate Complexes: Relevance to the Fe-Containing Nitrile Hydratases |
| 作品名稱（其他語言） | |
| 著者 | Lee, Chien-Ming; Hsieh, Chung-Hung; Dutta Amitava; Lee, Gene-Hsiang; 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 | Journal of the American Chemical Society 125(38), pp.11492-11493 |
| 摘要 | Iron−nitrosyl complex containing S-bonded monosulfinate [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (3) has been isolated from sulfur oxygenation of complex [PPN][(NO)Fe(S,S-C6H4)2] (2) which is obtained from addition of NO molecule to [PPN][(C4H8O)Fe(S,S-C6H4)2] (1) in organic solvents. This result reveals that binding of NO to the iron center promotes sulfur oxygenation of iron dithiolates by dioxygen and stabilizes the S-bonded sulfinate iron species. Analysis of the bond angles for complexes 2 and 3 reveals that iron is best described as existing in a distorted trigonal bipyramidal coordination environment surrounded by one NO, three thiolates, and one sulfinate in complex 3, whereas the distorted square pyramidal geometry is adopted in complex 2. Complex 3 further reacts in organic solvents with molecular oxygen in the presence of [PPN][NO2] to produce the dinuclear bis(sulfinate) complex [PPN]2[(NO)Fe(SO2,SO2-C6H4)(S,S-C6H4)]2 (4). Complex 3 showed reaction with PPh3 in THF/CH2Cl2 to yield complex 2 and Ph3PO. Upon photolysis of CH2Cl2 solution of complex 3 under N2 purge at ambient temperature, the UV−vis and IR spectra consistent with the formation of complex 2 demonstrate that complex 2 and 3 are photochemically interconvertible. Obviously, complex 3 is thermally quite stable but is photochemically active toward [O] release. Also described are the X-ray crystal structures of 3 and 4. |
| 關鍵字 | |
| 語言 | en |
| ISSN | 0002-7863 1520-5126 |
| 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/987654321/97587 ) |
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