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The oxidation of cyclo-olefin by the S = 2 ground-state complex [FeIV(O)(TQA)(NCMe)]2+

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Abstract

Density functional theory calculation is used to investigate the oxidation of cyclo-olefin (cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclo-octene) by the complex [FeIV(O)(TQA)(NCMe)]2+, which has S = 2 ground state, and the effect of electronic factors and steric hindrance on reaction barriers. Our results suggest that the oxo–iron(IV) complex can oxidise C–H and C = C bonds via a single-state mechanism, and two different ways of electron transport exist. The energy barriers initially decrease with increasing substrate size, and the trend then reverses. Comparison of the energy barrier in different systems reveals that except for the reaction between [FeIV(O)(TQA)(NCMe)]2+ and cycloheptene, oxo–iron(IV) complexes prefer epoxidation to hydroxylation. However, the hydroxylated product is more stable than the corresponding epoxidated product. This result indicates that the products of epoxidation tend to decompose first. The energy barrier of hydroxylation and epoxidation originates from the balance of orbital interaction and Pauli repulsion from the equatorial ligand and protons on the approaching substrate. In this regard, we calculate the weak interaction between two fragments (oxo–iron complex and substrates) using the independent gradient model and drawn the corresponding 3D isosurface representations of reactants.

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Acknowledgements

This work was supported by Natural Science Foundation of Liaoning Province (Grant 20180550765), the Open Project of SKLMRD (Open Project of State Key Laboratory of Molecular Reaction Dynamics), and National Natural Science Foundation of China (Grant 31771914). The results of quantum chemical calculations described in this paper were obtained on the homemade Linux cluster of group 1101, Dalian Institute of Chemical Physics.

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Authors and Affiliations

  1. School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, People’s Republic of China

    Zixian Li, Yi Wang, Wenzhi Li, Qingyue Li, Ziqing Gao, Jing Tian & Liang Dong

  2. COFCO Nutrition and Health Research Institute Co., Ltd, Beijing, 100020, People’s Republic of China

    Fan Li

  3. Lab Analyst of Network Information Center, Dalian Polytechnic University, Dalian, 116034, People’s Republic of China

    Xu Fei

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  1. Zixian Li
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Li, Z., Wang, Y., Li, W. et al. The oxidation of cyclo-olefin by the S = 2 ground-state complex [FeIV(O)(TQA)(NCMe)]2+. J Biol Inorg Chem 25, 371–382 (2020). https://doi.org/10.1007/s00775-020-01768-1

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