A Nonheme Sulfur-Ligated {FeNO} Complex and Comparison with Redox-Interconvertible {FeNO} and {FeNO} Analogues.

A nonheme {FeNO} complex, [Fe(NO)(N3PyS)] , was synthesized by reversible, one-electron oxidation of an {FeNO} analogue. This complex completes the first known series of sulfur-ligated {FeNO} complexes. All three {FeNO} complexes are readily interconverted by one-electron oxidation/reduction. A comparison of spectroscopic data (UV/Vis, NMR, IR, Mössbauer, X-ray absorption) provides a complete picture of the electronic and structural changes that occur upon {FeNO} -{FeNO} interconversion. Dissociation of NO from the new {FeNO} complex is shown to be controlled by solvent, temperature, and photolysis, which is rare for a sulfur-ligated {FeNO} species.