What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe-IV(L-ax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+)

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	What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe-IV(L-ax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+)
	Wang Yi 1; Liu Yuan 1; Yang Kun 3; He Zhengwen 1; Tian Jing 1; Xu, Fei 1; Guo Hong 1; Wang Yong 2
刊名	Journal of Biological Inorganic Chemistry
	2015
卷号	20 期号:7 页码:1123-1134
关键词	Non-heme Steric hindrance Hydroxylation Epoxidation Density functional theory
ISSN号	0949-8257
通讯作者	Wang Yi ; Wang Yong
英文摘要	Density functional theory is used to investigate geometric structures and mechanisms for hydroxylation and epoxidation from propene for four non-heme iron complexes, [Fe^IV(L_ax)(TMC)(O)]ⁿ⁺, which are the inverted isomers of [Fe^IV(O)(TMC)(L_ax)]ⁿ⁺ (L_ax = acetonitrile (AN), monoanionic trifluoroacetate (TF), azide (N3), thiolate (SR)). The Fe(IV)O unit is found to be sterically less hindered in [Fe^IV(L_ax)(TMC)(O)]ⁿ⁺ than that in [Fe^IV(O)(TMC)(L_ax)]ⁿ⁺. Becke, three-parameter, Lee–Yang–Parr (B3LYP) calculations show that hydroxylation and epoxidation proceed via a two-state-reactivity on competing triplet and quintet spin surfaces; and the reactions have been invariably mediated by the S = 2 state. The reaction pathways computed reveal that 2-AN is the most reactive in the four [Fe^IV(L_ax)(TMC)(O)]ⁿ⁺ complexes; along the reaction pathway, the axial ligand moves away from the iron center, and thus, the energy of the LUMO decreases. The anionic axial ligand, which is more electron releasing than neutral AN, shows a strong overlap of iron orbitals. Thus, the anionic ligand does not move away from the iron center. The H-abstraction is affected by the tunneling contribution, the more electron donation power of the axial ligand, the more effect of the tunneling contribution. Adding the tunneling correction, the relative reactivity of the hydroxylation follows the trend: 2-AN > 2-SR ≈ 2-N3 > 2-TF. However, for the epoxidation, the reactivity is in the following order of 2-AN > 2-TF > 2-N3 > 2-SR. Except for 2-AN, 2-X (L_ax = TF, N3, SR) complexes chemoselectively hydroxylate even in the presence of a C=C double bond.
学科主题	物理化学与绿色催化
收录类别	SCI
资助信息	L2013214 (the education department of Liaoning Province);Open Project of SKLMRD-K201511 (Open Project of State Key Laboratory of Molecular Reaction Dynamics)
语种	英语
WOS记录号	WOS:000362953900004
公开日期	2015-12-24
内容类型	期刊论文
源URL	[http://210.77.64.217/handle/362003/18759]
专题	兰州化学物理研究所_OSSO国家重点实验室
作者单位	1.Dalian Polytech Univ, Sch Biol Engn, Dalian 116034, Peoples R China 2.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China 3.Dalian Maritime Univ, Dept Phys, Dalian 116026, Peoples R China
推荐引用方式 GB/T 7714	Wang Yi,Liu Yuan,Yang Kun,et al. What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe-IV(L-ax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+)[J]. Journal of Biological Inorganic Chemistry,2015,20(7):1123-1134.
APA	Wang Yi.,Liu Yuan.,Yang Kun.,He Zhengwen.,Tian Jing.,...&Wang Yong.(2015).What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe-IV(L-ax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+).Journal of Biological Inorganic Chemistry,20(7),1123-1134.
MLA	Wang Yi,et al."What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe-IV(L-ax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+)".Journal of Biological Inorganic Chemistry 20.7(2015):1123-1134.