Reaction channels of iron-oxo and iron-imido molecular intermediates.
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| Title: | Reaction channels of iron-oxo and iron-imido molecular intermediates. |
|---|---|
| Authors: | Jones, Thomas D.1 (AUTHOR) djenki15@utk.edu, Brothers, Henry R.1 (AUTHOR), Pate-Geames, Elokkin K.1 (AUTHOR), Jenkins, David M.1 (AUTHOR), Vogiatzis, Konstantinos D.1 (AUTHOR) |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. 4/21/2026, Vol. 55 Issue 15, p5863-5876. 14p. |
| Subjects: | Iron catalysts, Iron oxidation, Carbon-hydrogen bonds, Aziridination, Epoxidation |
| Abstract: | Non-heme Fe(IV)-oxo intermediates are integral components of many enzymatic and homogeneous catalytic cycles, where they serve as key oxidants that enable challenging transformations. Numerous studies have focused on developing biomimetic non-heme Fe(IV)-oxo catalysts, elucidating their electronic structures, and understanding the nature of their reactivity. Their high-valent nature endows them with the capacity to perform demanding oxidative transformations, as evidenced by their broad application in C–H activation and alkene epoxidation chemistry. The isoelectronic Fe(IV)-imido analogue is much less studied, presenting significant opportunities for catalyst development in nitrene-transfer chemistry, including C–H amination and alkene aziridination. Mechanistically, nitrene transfer involves an Fe-imido intermediate featuring an N-centered radical. Two competing pathways have been described: a σ-channel and a π-channel, defined by whether the radical character is localized in a σ* or π* orbital. Similar to Fe(IV)-oxo chemistry, the reaction channel preference among Fe(IV)-imido catalysts plays a crucial role in determining their reactivities and selectivities. Herein, the nitrene transfer pathways for these species within both reaction channels are explored and comparative examples between Fe(IV)-oxo and Fe(IV)-imido catalysts are discussed. [ABSTRACT FROM AUTHOR] |
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| Database: | Engineering Source |
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