Oxygen Binding to Sulfur in Nitrosylated Iron−Thiolate Complexes:  Relevance to the Fe-Containing Nitrile Hydratases

doi:10.1021/ja035292t

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Title:	Oxygen Binding to Sulfur in Nitrosylated Iron−Thiolate Complexes: Relevance to the Fe-Containing Nitrile Hydratases
Authors:	Lee, Chien-Ming;Hsieh, Chung-Hung;Dutta Amitava;Lee, Gene-Hsiang;Liaw, Wen-Feng
Contributors:	淡江大學化學學系
Date:	2003-09
Issue Date:	2014-03-27 15:54:24 (UTC+8)
Publisher:	Washington, DC: American Chemical Society
Abstract:	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.
Relation:	Journal of the American Chemical Society 125(38), pp.11492-11493
DOI:	10.1021/ja035292t
Appears in Collections:	[Graduate Institute & Department of Chemistry] Journal Article

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