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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?
Wang, Yi; Wang, Yong; Han, Keli
KeywordNon-heme Hydroxylation Density Functional Calculations
Source PublicationJOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
2009-05-01
DOI10.1007/s00775-009-0468-x
Volume14Issue:4Pages:533-545
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Life Sciences & Biomedicine ; Physical Sciences
WOS SubjectBiochemistry & Molecular Biology ; Chemistry, Inorganic & Nuclear
WOS Research AreaBiochemistry & Molecular Biology ; Chemistry
WOS KeywordNONHEME 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
AbstractDensity 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.
Language英语
WOS IDWOS:000265397800005
Citation statistics
Cited Times:8[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/141529
Collection中国科学院大连化学物理研究所
AffiliationChinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
Recommended Citation
GB/T 7714
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.
APA Wang, Yi,Wang, Yong,&Han, Keli.(2009).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?.JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY,14(4),533-545.
MLA Wang, Yi,et al."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?".JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY 14.4(2009):533-545.
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