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题名: Theoretical study of cyclohexane hydroxylation by three possible isomers of [Fe-IV(O)(R-TPEN)](2+): does the pentadentate ligand wrapping around the metal center differently lead to the different stability and reactivity?
作者: Wang, Yi1;  Wang, Yong1;  Han, Keli1
关键词: Non-heme ;  Hydroxylation ;  Density functional calculations
刊名: JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
发表日期: 2009-05-01
DOI: 10.1007/s00775-009-0468-x
卷: 14, 期:4, 页:533-545
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Life Sciences & Biomedicine ;  Physical Sciences
类目[WOS]: Biochemistry & Molecular Biology ;  Chemistry, Inorganic & Nuclear
研究领域[WOS]: Biochemistry & Molecular Biology ;  Chemistry
英文摘要: Density functional theory calculations have been carried out to elucidate the mechanism of cyclohexane hydroxylation by three possible isomers of [Fe-IV(O)(N-R-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine)](2+) (R is methyl or benzyl) (Klinker et al. in Angew Chem Int Ed 44:3690-3694, 2005). The calculations offer a mechanistic view and reveal the following features: (a) all the three isomers possess triplet ground states and low-lying quintet excited states, (b) the relative stability follows the order isomer A > isomer B > isomer C, in agreement with the conclusions of Klinker et al., (c) the theoretical investigations provide a rationale to explain the interconversion of the three isomers, (d) the reaction pathways of the C-H hydroxylation are initiated by a hydrogen-abstraction step, and (e) the three isomers react with cyclohexane via two-state-reactivity patterns on competing triplet and quintet spin-state surfaces. As such, in the gas phase, the relative reactivity exhibits the trend isomer B > isomer A, while at the highest level, B2//B1 with zero point energy and solvation corrections, the relative reactivity follows the order isomer B > isomer A > isomer C. Thus, the calculated reaction pathway shows that pyridine rings perpendicular to the Fe-O axis result in more reactive species, and a pyridine ring coordinated trans to the oxygen atom leads to the least reactive isomer.
关键词[WOS]: NONHEME IRON ENZYMES ;  C-H HYDROXYLATION ;  TAURINE/ALPHA-KETOGLUTARATE DIOXYGENASE ;  DENSITY-FUNCTIONAL THERMOCHEMISTRY ;  HYDROGEN-ATOM ABSTRACTION ;  SPIN FE(IV) COMPLEX ;  FE-IV=O COMPLEXES ;  ELECTRONIC-STRUCTURES ;  2-STATE REACTIVITY ;  SPECTROSCOPIC CHARACTERIZATION
语种: 英语
WOS记录号: WOS:000265397800005
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/141529
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.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

Recommended Citation:
Wang, Yi,Wang, Yong,Han, Keli. Theoretical study of cyclohexane hydroxylation by three possible isomers of [Fe-IV(O)(R-TPEN)](2+): does the pentadentate ligand wrapping around the metal center differently lead to the different stability and reactivity?[J]. JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY,2009,14(4):533-545.
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