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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?

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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+ (Me2N 5), 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. Me2N 5 is energetically comparable with the cyclic ferric peracetate species Me2N 6, while in the pristine Fe(PDP) catalyst system, H 6 is more stable than H 5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N 5 and Me2N 6, Me2N 5 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.

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Acknowledgements

The authors acknowledge the financial support received from the National Natural Science Foundation of China (Project Nos. 21003116, 21173211, 21203218 and 21633013) and from the open fund of the State Key Laboratory of Molecular Reaction Dynamics (Project No. SKLMRD-K201715). The authors also gratefully acknowledge the computing resources and time made available by the Supercomputing Center of Cold and Arid Region Environment and the Engineering Research Institute of the Chinese Academy of Sciences.

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  1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, People’s Republic of China

    Fang Wang, Wei Sun, Chungu Xia & Yong Wang

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  1. Fang Wang
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Correspondence to Yong Wang.

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775_2017_1477_MOESM1_ESM.pdf

The mechanistic details are presented in 12 figures and 10 tables. Cartesian coordinates of all involved complexes are also given. (PDF 3776 kb)

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Wang, F., Sun, W., Xia, C. 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 Biol Inorg Chem 22, 987–998 (2017). https://doi.org/10.1007/s00775-017-1477-9

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