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题名: Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study
作者: Wang, Yi1, 2;  Han, Keli1
通讯作者: 韩克利
关键词: Non-heme ;  Hydrogen abstraction ;  Isomer ;  Density functional theory
刊名: JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
发表日期: 2010-03-01
DOI: 10.1007/s00775-009-0607-4
卷: 15, 期:3, 页:351-359
收录类别: SCI
文章类型: Article
部门归属: 11
项目归属: 1101
产权排名: 1;1
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: The geometric structures and mechanisms for hydrogen abstraction from cyclohexane for four high-valent complexes, [Fe(IV)(O)(TMC)(NCMe)](2+) (where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; 1-NCMe), the inverted isomer [Fe(IV)(NCMe)(TMC)(O)](2+) (2-NCMe), [Ru(IV)(O)(TMC)(NCMe)](2+) (the ruthenium analogue of 1-NCMe; 3-NCMe), and the inverted isomer [Ru(IV)(NCMe)(TMC)(O)](2)+ (4-NCMe), were investigated using density functional theory. The axial NCMe ligand was found to be sterically more hindered in 2-NCMe than in 1-NCMe, which is in accord with the calculated results that the Fe-L(axial) distance is longer in the former. Both 1-NCMe and 2-NCMe are capable of hydrogen abstraction from cyclohexane via two-state reactivity patterns. In contrast, 3-NCMe and 4-NCMe react with cyclohexane by a single-state mechanism. The reaction pathways computed reveal that 2-NCMe is more reactive than 1-NCMe, in agreement with experimental results, whereas the reactivity of 3-NCMe and 4-NCMe shows little dependence on whether the oxo unit is syn or anti to the four N-methyl groups. Our analysis shows that along the reaction pathway for 2-NCMe in the triplet spin state, the NCMe ligand moves away from the iron center, and therefore the energy of the sigma(z)*(2) (alpha-spin) orbital decreases and an electron is transferred to this orbital. Finally, we calculated the kinetic isotope effect and investigated the relationship between this effect and reaction barriers.
关键词[WOS]: NONHEME FE-IV=O ;  IRON ACTIVE-SITES ;  C-H HYDROXYLATION ;  ELECTRONIC-STRUCTURES ;  2-STATE REACTIVITY ;  DIOXYGEN ACTIVATION ;  RUTHENIUM PORPHYRIN ;  SPECTROSCOPIC CHARACTERIZATION ;  IRON(IV)-OXO COMPLEXES ;  OXOIRON(IV) COMPLEXES
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000275104400006
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/103043
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
2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China

Recommended Citation:
Wang, Yi,Han, Keli. Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study[J]. JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY,2010,15(3):351-359.
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