Reaction channels of iron-oxo and iron-imido molecular intermediates.
Saved in:
| 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] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
|---|---|
| Header | DbId: egs DbLabel: Engineering Source An: 193142945 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Reaction channels of iron-oxo and iron-imido molecular intermediates. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Jones%2C+Thomas+D%2E%22">Jones, Thomas D.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> djenki15@utk.edu</i><br /><searchLink fieldCode="AR" term="%22Brothers%2C+Henry+R%2E%22">Brothers, Henry R.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Pate-Geames%2C+Elokkin+K%2E%22">Pate-Geames, Elokkin K.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jenkins%2C+David+M%2E%22">Jenkins, David M.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Vogiatzis%2C+Konstantinos+D%2E%22">Vogiatzis, Konstantinos D.</searchLink><relatesTo>1</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 4/21/2026, Vol. 55 Issue 15, p5863-5876. 14p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Iron+catalysts%22">Iron catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Iron+oxidation%22">Iron oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Carbon-hydrogen+bonds%22">Carbon-hydrogen bonds</searchLink><br /><searchLink fieldCode="DE" term="%22Aziridination%22">Aziridination</searchLink><br /><searchLink fieldCode="DE" term="%22Epoxidation%22">Epoxidation</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=193142945 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/d5dt02942b Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 14 StartPage: 5863 Subjects: – SubjectFull: Iron catalysts Type: general – SubjectFull: Iron oxidation Type: general – SubjectFull: Carbon-hydrogen bonds Type: general – SubjectFull: Aziridination Type: general – SubjectFull: Epoxidation Type: general Titles: – TitleFull: Reaction channels of iron-oxo and iron-imido molecular intermediates. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Jones, Thomas D. – PersonEntity: Name: NameFull: Brothers, Henry R. – PersonEntity: Name: NameFull: Pate-Geames, Elokkin K. – PersonEntity: Name: NameFull: Jenkins, David M. – PersonEntity: Name: NameFull: Vogiatzis, Konstantinos D. IsPartOfRelationships: – BibEntity: Dates: – D: 21 M: 04 Text: 4/21/2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 55 – Type: issue Value: 15 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
| ResultId | 1 |
