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A Nonheme Sulfur-Ligated {FeNO}6 Complex and Comparison with Redox-Interconvertible {FeNO}7 and {FeNO}8 Analogues.

ABSTRACT: A nonheme {FeNO}6 complex, [Fe(NO)(N3PyS)]2+ , was synthesized by reversible, one-electron oxidation of an {FeNO}7 analogue. This complex completes the first known series of sulfur-ligated {FeNO}6-8 complexes. All three {FeNO}6-8 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}6 -{FeNO}8 interconversion. Dissociation of NO from the new {FeNO}6 complex is shown to be controlled by solvent, temperature, and photolysis, which is rare for a sulfur-ligated {FeNO}6 species.

SUBMITTER: Dey A

PROVIDER: S-EPMC6576265 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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A Nonheme Sulfur-Ligated {FeNO}6 Complex and Comparison with Redox-Interconvertible {FeNO}7 and {FeNO}8 Analogues.

Dey Aniruddha A Confer Alex M AM Vilbert Avery C AC Moënne-Loccoz Pierre P Lancaster Kyle M KM Goldberg David P DP

Angewandte Chemie (International ed. in English) 20180917 41

A nonheme {FeNO}6 complex, [Fe(NO)(N3PyS)]2+ , was synthesized by reversible, one-electron oxidation of an {FeNO}7 analogue. This complex completes the first known series of sulfur-ligated {FeNO}6-8 complexes. All three {FeNO}6-8 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 structura ...[more]

PMID: 30125450

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Project description:Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes and their biomimetic compounds. Here, we report mononuclear nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)FeIII(O2)]+-M3+ (M3+ = Sc3+ and Y3+; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), which are characterized spectroscopically as a 'side-on' iron(III)-peroxo complex binding a redox-inactive metal ion, (TMC)FeIII-(?,?2:?2-O2)-M3+ (2-M). While an iron(III)-peroxo complex, [(TMC)FeIII(O2)]+, does not react with electron donors (e.g., ferrocene), one-electron reduction of the iron(III)-peroxo complexes binding redox-inactive metal ions occurs readily upon addition of electron donors, resulting in the generation of an iron(IV)-oxo complex, [(TMC)FeIV(O)]2+ (4), via heterolytic O-O bond cleavage of the peroxide ligand. The rates of the conversion of 2-M to 4 are found to depend on the Lewis acidity of the redox-inactive metal ions and the oxidation potential of the electron donors. We have also determined the fundamental electron-transfer properties of 2-M, such as the reduction potential and the reorganization energy in electron-transfer reaction. Based on the results presented herein, we have proposed a mechanism for the reactions of 2-M and electron donors; the reduction of 2-M to the reduced species, (TMC)FeII-(O2)-M3+ (2'-M), is the rate-determining step, followed by heterolytic O-O bond cleavage of the reduced species to form 4. The present results provide a biomimetic example demonstrating that redox-inactive metal ions bound to an iron(III)-peroxo intermediate play a significant role in activating the peroxide O-O bond to form a high-valent iron(IV)-oxo species.

Dataset Information

A Nonheme Sulfur-Ligated {FeNO}6 Complex and Comparison with Redox-Interconvertible {FeNO}7 and {FeNO}8 Analogues.

Publications

A Nonheme Sulfur-Ligated {FeNO}<sup>6</sup> Complex and Comparison with Redox-Interconvertible {FeNO}<sup>7</sup> and {FeNO}<sup>8</sup> Analogues.

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