Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations
文献类型：期刊论文
| 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
 |
| 出版日期 | 2014 |
| 卷号 | 5 |
| 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. |
| 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 |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000331083800029 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/145662]  |
| 专题 | 大连化学物理研究所_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 |
| 推荐引用方式 GB/T 7714 | 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). |
入库方式： OAI收割
来源：大连化学物理研究所
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