摘要
Iron-nitrosyl complex containing S-bonded monosulfinate [PPN][(NO)Fe(S,SO 2 -C 6 H 4 )(S,S-C 6 H 4 )] (3) has been isolated from sulfur oxygenation of complex [PPN][(NO)Fe(S,S-C 6 H 4 ) 2 ] (2) which is obtained from addition of NO molecule to [PPN][(C 4 H 8 O)Fe(S,S-C 6 H 4 ) 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][NO 2 ] to produce the dinuclear bis(sulfinate) complex [PPN] 2 [(NO)Fe(SO 2 ,SO 2 -C 6 H 4 )(S,S-C 6 H 4 )] 2 (4). Complex 3 showed reaction with PPh 3 in THF/CH 2 Cl 2 to yield complex 2 and Ph 3 PO. Upon photolysis of CH 2 Cl 2 solution of complex 3 under N 2 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. Copyright © 2003 American Chemical Society.