Conversion of high-spin iron(III)-alkylperoxo to iron(IV)-oxo species via O-O bond homolysis in nonheme iron models
- 등재 SCIE, SCOPUS
- 발행기관 ROYAL SOC CHEMISTRY
- 발행년도 2014
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000086923
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/c3sc52236a
초록/요약
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 effect", which has been well established in heme enzymes. To the best of our knowledge, the present study reports the first clear example showing the O-O bond homolysis of a high-spin iron(III)-alkylperoxo complex and the axial ligand effect on the alkylperoxo O-O bond cleavage in nonheme iron models.
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