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Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b08161· OSTI ID:1419655
 [1];  [2];  [2];  [2];  [3];  [3];  [4];  [4];  [4];  [5];  [6]
  1. Ewha Womans Univ., Seoul (Korea); Sookmyung Women's Univ., Seoul (Korea)
  2. Ewha Womans Univ., Seoul (Korea)
  3. Univ. of Hyogo, Hyogo (Japan)
  4. Univ. Grenoble Alpes, Grenoble (France)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. Ewha Womans Univ., Seoul (Korea); Chinese Academy of Sciences, Lanzhou (China)
+ Show Author Affiliations

Here, 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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1419655
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 41 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Uncatalyzed Oxidative C−H Amination of 9,10‐Dihydro‐9‐Heteroanthracenes: A Mechanistic Study journal March 2019
A Two-Coordinate Iron(II) Imido Complex with NHC Ligation: Synthesis, Characterization, and Its Diversified Reactivity of Nitrene Transfer and C–H Bond Activation journal May 2019
Fe‐Based Complexes as Styrene Aziridination Catalysts: Ligand Substitution Tunes Catalyst Activity journal March 2019
A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies journal November 2018
Generation and Reactivity of a One‐Electron‐Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand journal August 2019
C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex journal January 2018
Understanding the differences between iron and palladium in cross-coupling reactions journal January 2019
Octahedral iron( iv )–tosylimido complexes exhibiting single electron-oxidation reactivity journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY