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题名: Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations
作者: Oloo, Williamson N.1, 2;  Meier, Katlyn K.3;  Wang, Yong4;  Shaik, Sason5, 6;  Muenck, Eckard3;  Que, Lawrence1, 2
刊名: NATURE COMMUNICATIONS
发表日期: 2014
DOI: 10.1038/ncomms4046
卷: 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
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.
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
语种: 英语
WOS记录号: WOS:000331083800029
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/145662
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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