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Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex
- Hong, Seungwoo, Lu, Xiaoyan, Lee, Yong-Min, Seo, Mi Sook, Ohta, Takehiro, Ogura, Takashi, Clémancey, Martin, Maldivi, Pascale, Latour, Jean-Marc, Sarangi, Ritimukta, Nam, Wonwoo
- Journal of the American Chemical Society 2017 v.139 no.41 pp. 14372-14375
- carbon-hydrogen bond activation, cations, chemical bonding, ferrimagnetic materials, iron, ligands, oxidants, oxidation
- 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.