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Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations
Oloo, Williamson N.1,2; Meier, Katlyn K.3; Wang, Yong4; Shaik, Sason5,6; Muenck, Eckard3; Que, Lawrence1,2
刊名NATURE COMMUNICATIONS
2014
DOI10.1038/ncomms4046
5
收录类别SCI
文章类型Article
WOS标题词Science & Technology
类目[WOS]Multidisciplinary Sciences
研究领域[WOS]Science & Technology - Other Topics
关键词[WOS]ELECTRON-PARAMAGNETIC-RESONANCE ; FE-IV=O COMPLEX ; C-H ; ENANTIOSELECTIVE EPOXIDATION ; ALKANE HYDROXYLATION ; BOND-CLEAVAGE ; EPR DETECTION ; ACETIC-ACID ; REACTIVITY ; H2O2
英文摘要Synthetically useful hydrocarbon oxidations are catalysed by bio-inspired non-heme iron complexes using hydrogen peroxide as oxidant, and carboxylic acid addition enhances their selectivity and catalytic efficiency. Talsi has identified a low-intensity g = 2.7 electron paramagnetic resonance signal in such catalytic systems and attributed it to an oxoiron(V)-carboxylate oxidant. Herein we report the use of Fe-II(TPA(star)) (TPA(star) = tris (3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) to generate this intermediate in 50% yield, and have characterized it by ultraviolet-visible, resonance Raman, Mossbauer and electrospray ionization mass spectrometric methods as a low-spin acylperoxoiron(III) species. Kinetic studies show that this intermediate is not itself the oxidant but decays via a unimolecular rate-determining step to unmask a powerful oxidant. The latter is shown by density functional theory calculations to be an oxoiron(V) species that oxidises substrate without a barrier. This study provides a mechanistic scenario for understanding catalyst reactivity and selectivity as well as a basis for improving catalyst design.
语种英语
WOS记录号WOS:000331083800029
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文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/145662
专题中国科学院大连化学物理研究所
作者单位1.Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
2.Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA
3.Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
4.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
5.Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel
6.Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel
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Oloo, Williamson N.,Meier, Katlyn K.,Wang, Yong,et al. Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations[J]. NATURE COMMUNICATIONS,2014,5.
APA Oloo, Williamson N.,Meier, Katlyn K.,Wang, Yong,Shaik, Sason,Muenck, Eckard,&Que, Lawrence.(2014).Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations.NATURE COMMUNICATIONS,5.
MLA Oloo, Williamson N.,et al."Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations".NATURE COMMUNICATIONS 5(2014).
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