Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction

[Image: see text] The iron(IV) nitrido complex PhB(MesIm)(3)Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)(3)Fe(η(5)-C(4)H(4)N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reac...

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Autores principales: Lee, Wei-Tsung, Juarez, Ruth A., Scepaniak, Jeremiah J., Muñoz, Salvador B., Dickie, Diane A., Wang, Haobin, Smith, Jeremy M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4139179/
https://www.ncbi.nlm.nih.gov/pubmed/25068927
http://dx.doi.org/10.1021/ic5010006
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author Lee, Wei-Tsung
Juarez, Ruth A.
Scepaniak, Jeremiah J.
Muñoz, Salvador B.
Dickie, Diane A.
Wang, Haobin
Smith, Jeremy M.
author_facet Lee, Wei-Tsung
Juarez, Ruth A.
Scepaniak, Jeremiah J.
Muñoz, Salvador B.
Dickie, Diane A.
Wang, Haobin
Smith, Jeremy M.
author_sort Lee, Wei-Tsung
collection PubMed
description [Image: see text] The iron(IV) nitrido complex PhB(MesIm)(3)Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)(3)Fe(η(5)-C(4)H(4)N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product.
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spelling pubmed-41391792015-07-28 Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction Lee, Wei-Tsung Juarez, Ruth A. Scepaniak, Jeremiah J. Muñoz, Salvador B. Dickie, Diane A. Wang, Haobin Smith, Jeremy M. Inorg Chem [Image: see text] The iron(IV) nitrido complex PhB(MesIm)(3)Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)(3)Fe(η(5)-C(4)H(4)N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product. American Chemical Society 2014-07-28 2014-08-18 /pmc/articles/PMC4139179/ /pubmed/25068927 http://dx.doi.org/10.1021/ic5010006 Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html)
spellingShingle Lee, Wei-Tsung
Juarez, Ruth A.
Scepaniak, Jeremiah J.
Muñoz, Salvador B.
Dickie, Diane A.
Wang, Haobin
Smith, Jeremy M.
Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title_full Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title_fullStr Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title_full_unstemmed Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title_short Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction
title_sort reaction of an iron(iv) nitrido complex with cyclohexadienes: cycloaddition and hydrogen-atom abstraction
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4139179/
https://www.ncbi.nlm.nih.gov/pubmed/25068927
http://dx.doi.org/10.1021/ic5010006
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