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Title: 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
ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3];  [3];  [4];  [4];  [4];  [5]; ORCiD logo [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)

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; ANR-11-LABX-003; NRF-2010-00353; NRF-2012R1A3A2048842; NRF-2017R1C1B2002037; 15H00960; P41GM103393
OSTI ID:
1419655
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 41; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 40 works
Citation information provided by
Web of Science

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Cited By (8)

C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex journal January 2018
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
Uncatalyzed Oxidative C−H Amination of 9,10‐Dihydro‐9‐Heteroanthracenes: A Mechanistic Study journal March 2019
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
Generation and Reactivity of a One‐Electron‐Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand journal August 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

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