| 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+) | |
| Department | OSSO国家重点实验室 |
| Wang Yi1; Liu Yuan1; Yang Kun3; He Zhengwen1; Tian Jing1; Xu, Fei1; Guo Hong1; Wang Yong2 | |
| 2015 | |
| Source Publication | Journal of Biological Inorganic Chemistry
 |
| ISSN | 0949-8257 |
| Volume | 20Issue:7Pages:1123-1134 |
| Abstract | Density functional theory is used to investigate geometric structures and mechanisms for hydroxylation and epoxidation from propene for four non-heme iron complexes, [FeIV(Lax)(TMC)(O)]n+, which are the inverted isomers of [FeIV(O)(TMC)(Lax)]n+ (Lax = acetonitrile (AN), monoanionic trifluoroacetate (TF), azide (N3), thiolate (SR)). The Fe(IV)O unit is found to be sterically less hindered in [FeIV(Lax)(TMC)(O)]n+ than that in [FeIV(O)(TMC)(Lax)]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 [FeIV(Lax)(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 (Lax = TF, N3, SR) complexes chemoselectively hydroxylate even in the presence of a C=C double bond. |
| Keyword | Non-heme Steric Hindrance Hydroxylation Epoxidation Density Functional Theory |
| Subject Area | 物理化学与绿色催化 |
| DOI | 10.1007/s00775-015-1294-y |
| Funding Organization | L2013214 (the education department of Liaoning Province);Open Project of SKLMRD-K201511 (Open Project of State Key Laboratory of Molecular Reaction Dynamics) |
| Indexed By | SCI |
| If | 2.538 |
| Language | 英语 |
| compositor | 第二作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/18759 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Wang Yi; Wang Yong |
| Affiliation | 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 |
| Recommended Citation 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. |
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| 20151123-1134.pdf（4174KB） | 期刊论文 | 出版稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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