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  1. Free, publicly-accessible full text available April 10, 2024
  2. null (Ed.)
  3. Abstract

    A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+(1), is synthesized and characterized structurally and spectroscopically. While1is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly,1shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that1has an amphoteric reactivity. Another interesting observation is that1can be used as an oxygen atom donor in the generation of high‐valent metal‐oxo complexes. To our knowledge, we present the first crystal structure of a CoIIIiodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.

     
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  4. Abstract

    A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+(1), is synthesized and characterized structurally and spectroscopically. While1is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly,1shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that1has an amphoteric reactivity. Another interesting observation is that1can be used as an oxygen atom donor in the generation of high‐valent metal‐oxo complexes. To our knowledge, we present the first crystal structure of a CoIIIiodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.

     
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  5. Abstract

    A mononuclear nonheme manganese(IV)–oxo complex binding the Ce4+ion, [(dpaq)MnIV(O)]+–Ce4+(1‐Ce4+), was synthesized by reacting [(dpaq)MnIII(OH)]+(2) with cerium ammonium nitrate (CAN).1‐Ce4+was characterized using various spectroscopic techniques, such as UV/Vis, EPR, CSI‐MS, resonance Raman, XANES, and EXAFS, showing an Mn−O bond distance of 1.69 Å with a resonance Raman band at 675 cm−1. Electron‐transfer and oxygen atom transfer reactivities of1‐Ce4+were found to be greater than those of MnIV(O) intermediates binding redox‐inactive metal ions (1‐Mn+). This study reports the first example of a redox‐active Ce4+ion‐bound MnIV‐oxo complex and its spectroscopic characterization and chemical properties.

     
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