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

High valent iron terminal imido species (FeNR) have been shown to be key reactive intermediates in C–H functionalization. However, the detailed structure–reactivity relationship in FeNR species derived from studies of structurally well-characterized high-valent FeNR complexes are still scarce, an...

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Veröffentlicht in:Chemical science (Cambridge) Jg. 14; H. 11; S. 2808 - 2820
Hauptverfasser: Xiong, Jin, Liu, Qing, Lavina, Barbara, Hu, Michael Y., Zhao, Jiyong, Alp, Esen E., Deng, Liang, Ye, Shengfa, Guo, Yisong
Format: Journal Article
Sprache:Englisch
Veröffentlicht: England Royal Society of Chemistry 15.03.2023
Royal Society of Chemistry (RSC)
The Royal Society of Chemistry
Schlagworte:
Chemistry
Congeners
Electron spin
Electronic structure
Iron
Polarization (spin alignment)
ISSN:2041-6520, 2041-6539
Online-Zugang:Volltext
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Zusammenfassung:High valent iron terminal imido species (FeNR) have been shown to be key reactive intermediates in C–H functionalization. However, the detailed structure–reactivity relationship in FeNR species derived from studies of structurally well-characterized high-valent Fe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(CF 3 ) 2 Ph) 2 ] (2), and two closely related S = 0 congeners bearing alkyl and aryl substituents, [(IPr)Fe(NC(CMe 3 ) 2 Ph) 2 ] (3) and [(IPr)Fe(NDipp) 2 ] (1), respectively. Compared with 1 and 3, 2 exhibits a decreased Fe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.
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USDOE
GUP-60939, GUP-68490, and GUP-73059
ISSN:2041-6520
2041-6539
DOI:10.1039/D2SC06273A