DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species? | |
Department | 苏州研究院 |
Wang F(王芳); Sun W(孙伟); Xia CG(夏春谷); Wang Y(王永); Wang Y(王永) | |
The second department | osso国家重点实验室 |
2017 | |
Source Publication | Journal of Biological Inorganic Chemistry |
ISSN | 0949-8257 |
Volume | 22Issue:7Pages:987-998 |
Abstract | Through the introduction of dimethylamino (Me2N) substituent at the pyridine ring of 2-((R)-2-[(R)-1-(pyridine-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-ylmethyl)pyridine (PDP) ligand, the non-heme FeII(Me2NPDP)/H2O2/AcOH catalyst system was found to exhibit significant higher catalytic activity and enantioselectivity than the non-substituent one in the asymmetric epoxidation experiments. The mechanistic origin of the remarkable substituent effects in these oxidation reactions has not been well established. To ascertain the potent oxidant and the related reaction mechanism, a detailed DFT calculation was performed. Interestingly, a novel Fe(IV)-oxo Me2NPDP cation radical species, [(Me2NPDP)+·FeIV(O)(OAc)]2+ (Me2N5), with about one spin spreading over the non-heme Me2NPDP ligand was formed via a carboxylic-acid-assisted O–O bond heterolysis, which is reminiscent of Compound I (an Fe(IV)(O)(porphyrin cation radical) species) in cytochrome P450 chemistry. Me2N5 is energetically comparable with the cyclic ferric peracetate species Me2N6, while in the pristine Fe(PDP) catalyst system, H6 is more stable than H5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N5 and Me2N6, Me2N5 is supposed as the true oxidant triggering the epoxidation of olefins. In addition, a systematic research on the substituent effects varied from the electron-donating substituent (dMM, the substituents at sites 3, 4, and 5 of the pyridine ring: methyl, methoxyl, and methyl) to the electron-withdrawing one (CF3, 2,6-bis(trifluoromethyl)phenyl) on the electronic structure of the reaction intermediates has also been investigated. An alternative cyclic ferric peracetate complex is obtained, indicating that the substituents at the pyridine ring of PDP ligands have significant impacts on the electronic structure of the oxidants. |
Keyword | Non-heme Iron Epoxidation Density Functional Theory Substituent Effect Cation Radical Species |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1007/s00775-017-1477-9 |
Funding Organization | the National Natural Science Foundation of China (Project Nos. 21003116;21173211;21203218;21633013);the open fund of the State Key Laboratory of Molecular Reaction Dynamics (Project No. SKLMRD-K201715) |
Indexed By | SCI |
If | 2.894 |
Language | 英语 |
Funding Project | 仿生与生物催化研究组;均相催化研究组 |
compositor | 第一作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/22502 |
Collection | 苏州研究院 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Wang Y(王永) |
Affiliation | Chinese Acad Sci, Lanzhou Inst Chem Phys, Suzhou Res Inst, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China |
Recommended Citation GB/T 7714 | Wang F,Sun W,Xia CG,et al. DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?[J]. Journal of Biological Inorganic Chemistry,2017,22(7):987-998. |
APA | Wang F,Sun W,Xia CG,Wang Y,&王永.(2017).DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?.Journal of Biological Inorganic Chemistry,22(7),987-998. |
MLA | Wang F,et al."DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?".Journal of Biological Inorganic Chemistry 22.7(2017):987-998. |
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