Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(lll)-Hydroperoxo Complex.

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)—peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(TMC)(OOH)]. The Mn-hydroperoxo intermediate is characterized with various spectroscopic...

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Publicado en:Journal of the American Chemical Society Vol. 136; no. 35; pp. 12229 - 12233
Autores principales: Hee So, Young Jun Park, Kyung-Bin Cho, Yong-Min Lee, Mi Sook Seo, Jaeheung Cho, Sarangi, Ritimukta, Wonwoo Nam
Formato: Artículo
Publicado: American Chemical Society 9/3/2014
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      dt: 9/3/2014
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      pub: American Chemical Society
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        10.1021/ja506275q
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        atl: Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(lll)-Hydroperoxo Complex.
      aug:
        au:
          Hee So
          Young Jun Park
          Kyung-Bin Cho
          Yong-Min Lee
          Mi Sook Seo
          Jaeheung Cho
          Sarangi, Ritimukta
          Wonwoo Nam
        affil:
          Department of Chemistry & Nano Science, Ewha Womans University, Seoul 120-750, Korea
          Department of Emerging Materials Science, DGIST, Daegu 711-873, Korea
          Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025-7015, United States
      su:
        Reactivity (Chemistry)
        Manganese compounds
        Proton transfer reactions
        Intermediates (Chemistry)
        Electrophiles
        Oxidizing agents
        Ligands (Chemistry)
        Density functional theory
      sug:
        subj:
          Reactivity (Chemistry)
          Manganese compounds
          Proton transfer reactions
          Intermediates (Chemistry)
          Electrophiles
          Oxidizing agents
          Ligands (Chemistry)
          Density functional theory
      ab: We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)—peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(TMC)(OOH)]. The Mn-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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