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The C–H bond activation by non-heme oxidant [(N4Py)FeIV(O)]2+ with external electric field

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Abstract

The C–H bond activation by non-heme iron-oxo species is one of the most interesting fundamental steps in organic oxidation reactions. This work focuses on the C–H bond activation by an external electric field (EEF) in a non-heme complex. The hydrogen atom abstraction from 2,5-(MeO)2C6H3CH2OH by [(N4Py)FeIV(O)]2+ utilizing an EEF was studied using density functional theory. Our analysis suggests that the mechanism of this process can be characterized as a mixture of hydrogen atom transfer and concerted-asynchronous electron–proton transfer that can be modulated by the EEF. Our study demonstrates an EEF that decreases the reaction barrier by increasing the electron donor orbital energy, which facilitates electron transfer. The reaction finally becomes barrierless when the EEF is greater than 0.0045au. The finding from this work demonstrates the exciting possibility of tuning the reaction mechanism using the EEF.

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Acknowledgements

This work was supported by the National Science Foundation of China (Nos. 21503089) and China Postdoctoral Science Foundation (2015M581393). Z.X.Q. thanks Adam Grofe for constructive suggestions as well as the improvement in the manuscript.

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  1. Institute of Theoretical Chemistry and Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun, 130023, China

    Meng Wang & Zexing Qu

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  1. Meng Wang
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Wang, M., Qu, Z. The C–H bond activation by non-heme oxidant [(N4Py)FeIV(O)]2+ with external electric field. Theor Chem Acc 139, 64 (2020). https://doi.org/10.1007/s00214-020-2581-4

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