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A theoretical study for spin-dependent hydrogen abstraction by non-heme FeIVO complexes based on DFT potential energy surfaces

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Abstract

Extensive studies have been performed to reveal the mechanism of alkane hydroxylation by high-valent non-heme FeIVO species in TauD-J and synthetic complexes. However, the fundamental differences in mechanism based on spin state have not yet been fully understood. To explicate the mechanism at an atomistic level, DFT potential energy surfaces were calculated along the intrinsic reaction coordinate of hydrogen abstraction. The Fe–O bond length change and hydrogen atom transfer occur with high asynchronicity, and only quintet FeIVO complexes use a transient FeIII-oxyl species for hydrogen abstraction. TauD-J uses both the σ- and π-pathways for hydrogen transfer, rendering it more reactive than synthetic complexes. The quintet σ-pathway involves the donation of α-electrons to the \({\sigma }_{\mathrm{Fe}-\mathrm{O}}^{*}\) orbital from both axial ligands and the C–H bond, which produces the FeIII-oxyl species. However, electron donation from the axial ligands may impede further electron transfer from the C–H bond, disrupting the hydrogen transfer process and reducing the tunneling effect. Conversely, the \({\sigma }_{\mathrm{Fe}-\mathrm{O}}^{*}\) orbital in the triplet π-pathway accepts both α- and β-electrons from the axial ligands, resulting in a swift elongation of the Fe–O bond length without generating the FeIII-oxyl species. This process does not affect hydrogen transfer as the \({\pi }_{\mathrm{Fe}-\mathrm{O}}^{*}\) orbital receives electrons from the C–H bond. This distinction clarifies why the tunneling effect is greater in the triplet state. Overall, this research offers insight into the detailed mechanism of hydrogen abstraction, emphasizing the role of axial ligands and spin-dependent reactivity.

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Acknowledgements

This work was supported by a grant from Kyung Hee University (KHU-20190977).

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  1. Department of Applied Chemistry and Institute of Natural Sciences, Kyung Hee University, 1732 Deogyeong-daero, Giheung-Gu, Yongin-Si, 17104, Gyeonggi-Do, Korea

    Sumin Park, Binh Khanh Mai & Yongho Kim

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  1. Sumin Park
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  2. Binh Khanh Mai
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SP did most of the calculations for NBO analysis and made most of figures and tables. BKM calculated the PES along the minimum energy path. YK wrote and proofread the manuscript.

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Correspondence to Yongho Kim.

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Park, S., Mai, B.K. & Kim, Y. A theoretical study for spin-dependent hydrogen abstraction by non-heme FeIVO complexes based on DFT potential energy surfaces. Theor Chem Acc 142, 117 (2023). https://doi.org/10.1007/s00214-023-03059-9

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