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-Serre; Clemancey, M (Clemancey, Marti; Ogura, 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
- Pages
- 7
- 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
2041-6539
- 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
-
Go to Link
- Appears in
Collections - 이과대학 > 화학과 > 1. Journal Articles
Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.