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Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study
Wang, Yi1,2; Han, Keli1; Han KL(韩克利)
关键词Non-heme Hydrogen Abstraction Isomer Density Functional Theory
刊名JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
2010-03-01
DOI10.1007/s00775-009-0607-4
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
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
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.
语种英语
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WOS记录号WOS:000275104400006
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被引频次:14[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/103043
专题中国科学院大连化学物理研究所
通讯作者Han KL(韩克利)
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
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Wang, Yi,Han, Keli,Han KL. 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.
APA Wang, Yi,Han, Keli,&韩克利.(2010).Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study.JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY,15(3),351-359.
MLA Wang, Yi,et al."Steric hindrance effect of the equatorial ligand on Fe(IV)O and Ru(IV)O complexes: a density functional study".JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY 15.3(2010):351-359.
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