Seungwoo Hong1,2, Xiaoyan Lu1, Yong-Min Lee1, Mi Sook Seo1, Takehiro Ohta3, Takashi Ogura3, Martin Clémancey4, Pascale Maldivi5, Jean-Marc Latour4, Ritimukta Sarangi6, Wonwoo Nam1,7. 1. Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea. 2. Department of Chemistry, Sookmyung Women's University , Seoul 04310, Korea. 3. Picobiology Institute, Graduate School of Life Science, University of Hyogo, RSC-UH LP Center , Hyogo 679-5148, Japan. 4. LCBM/PMB and CEA/BIG/CBM/and CNRS UMR 5249, Université Grenoble Alpes , Grenoble 38054, France. 5. CEA, CNRS, INAC, SYMMES, Université Grenoble Alpes , Grenoble 38000, France. 6. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory , California 94025, United States. 7. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, China.
Abstract
A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [FeV(NTs)(TAML)]- (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [FeV(NTs)(TAML+•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML+•). 2 is a competent oxidant in C-H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.
A mononuclear nonhemen class="Chemical">iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [FeV(NTs)(TAML)]- (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [FeV(NTs)(TAML+•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML+•). 2 is a competent oxidant in C-H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.
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