Issue 11, 2023

Spin polarization assisted facile C–H activation by an S = 1 iron(iv)–bisimido complex: a comprehensive spectroscopic and theoretical investigation

Abstract

High valent iron terminal imido species (Fe[double bond, length as m-dash]NR) have been shown to be key reactive intermediates in C–H functionalization. However, the detailed structure–reactivity relationship in Fe[double bond, length as m-dash]NR species derived from studies of structurally well-characterized high-valent Fe[double bond, length as m-dash]NR complexes are still scarce, and the impact of imido N-substituents (electron-donating vs. electron-withdrawing) on their electronic structures and reactivities has not been thoroughly explored. In this study, we report spectroscopic and computational studies on a rare S = 1 iron(IV)–bisimido complex featuring trifluoromethyl groups on the imido N-substituents, [(IPr)Fe(NC(CF3)2Ph)2] (2), and two closely related S = 0 congeners bearing alkyl and aryl substituents, [(IPr)Fe(NC(CMe3)2Ph)2] (3) and [(IPr)Fe(NDipp)2] (1), respectively. Compared with 1 and 3, 2 exhibits a decreased Fe[double bond, length as m-dash]NR bond covalency due to the electron-withdrawing and the steric effect of the N-substituents, which further leads to a pseudo doubly degenerate ground electronic structure and spin polarization induced β spin density on the imido nitrogens. This unique electronic structure, which differs from those of the well-studied Fe(IV)–oxido complexes and many previously reported Fe(IV)–imido complexes, provides both kinetic and thermodynamic advantages for facile C–H activation, compared to the S = 0 counterparts.

Graphical abstract: Spin polarization assisted facile C–H activation by an S = 1 iron(iv)–bisimido complex: a comprehensive spectroscopic and theoretical investigation

Supplementary files

Article information

Article type
Edge Article
Submitted
14 nóv. 2022
Accepted
14 feb. 2023
First published
15 feb. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 2808-2820

Spin polarization assisted facile C–H activation by an S = 1 iron(IV)–bisimido complex: a comprehensive spectroscopic and theoretical investigation

J. Xiong, Q. Liu, B. Lavina, M. Y. Hu, J. Zhao, E. E. Alp, L. Deng, S. Ye and Y. Guo, Chem. Sci., 2023, 14, 2808 DOI: 10.1039/D2SC06273A

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