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
國別 USA
公開徵稿
出版型式 紙本 電子版
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