Detailed Information

Cited 0 time in webofscience Cited 0 time in scopus
Metadata Downloads

Conversion of high-spin iron(III)-alkylperoxo to iron(IV)-oxo species via O-O bond homolysis in nonheme iron models

Authors
Hong, S (Hong, Seungwoo)Lee, YM (Lee, Yong-Min)Cho, KB (Cho, Kyung-Bin)Seo, MS (Seo, Mi Sook)Song, D (Song, Dayoung)Yoon, J (Yoon, Jihae)Garcia-Serres, R (Garcia-SerreClemancey, M (Clemancey, MartiOgura, T (Ogura, Takashi)Shin, W (Shin, Woonsup)Latour, JM (Latour, Jean-Marc)Nam, W (Nam, Wonwoo)...More...
Issue Date
Jan-2014
Publisher
ROYAL SOC CHEMISTRY
Citation
CHEMICAL SCIENCE, v.5, no.1, pp.156 - 162
Journal Title
CHEMICAL SCIENCE
Volume
5
Number
1
Start Page
156
End Page
162
URI
https://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/147369
DOI
10.1039/c3sc52236a
ISSN
2041-6520
Abstract
The mechanism of the alkylperoxo O-O bond cleavage of low-spin iron(III)-alkylperoxo species has been well established in nonheme iron models. In contrast, the alkylperoxo O-O bond cleavage in nonheme high-spin iron(III)-alkylperoxo species binding an axial ligand has yet to be elucidated. Herein, we report the synthesis and characterization of mononuclear nonheme high-spin iron(III)-alkylperoxo complexes each bearing an N-tetramethylated 13-membered macrocyclic ligand (13-TMC), [Fe-III(OOC(CH3)(3))-(13-TMC)](2+) and [Fe-III(OOC(CH3)(2)C6H5)(13-TMC)](2+). The high-spin iron(III)-alkylperoxo complexes were converted to an iron(IV)-oxo complex at a fast rate upon addition of thiocyanate (NCS ) via the formation of a short-lived intermediate. This intermediate was identified as a high-spin iron(III)alkylperoxo complex binding a thiocyanate ion as an axial ligand by characterizing it with various spectroscopic methods and density functional theory (DFT) calculations. We have also provided strong evidence that conversion of the high-spin iron(III)-alkylperoxo complex to its corresponding iron(IV)-oxo complex occurs via O-O bond homolysis. Thus, we have concluded that the role of the axial ligand binding to a high-spin iron(III)-alkylperoxo complex is to facilitate the alkylperoxo O-O bond cleavage via the " push effe
Files in This Item
There are no files associated with this item.
Appears in
Collections
이과대학 > 화학과 > 1. Journal Articles

qrcode

Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.

Related Researcher

Researcher Hong, Seung Woo photo

Hong, Seung Woo
이과대학 (화학과)
Read more

Altmetrics

Total Views & Downloads

BROWSE