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Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
The base metal complex Bu(4)N[Fe(CO)(3)(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5947516/ https://www.ncbi.nlm.nih.gov/pubmed/29861942 http://dx.doi.org/10.1039/c5sc02342d |
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author | Lin, Che-Hung Pursley, Dominik Klein, Johannes E. M. N. Teske, Johannes Allen, Jennifer A. Rami, Fabian Köhn, Andreas Plietker, Bernd |
author_facet | Lin, Che-Hung Pursley, Dominik Klein, Johannes E. M. N. Teske, Johannes Allen, Jennifer A. Rami, Fabian Köhn, Andreas Plietker, Bernd |
author_sort | Lin, Che-Hung |
collection | PubMed |
description | The base metal complex Bu(4)N[Fe(CO)(3)(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the [Fe(CO)(3)(NO)] anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial π-complex with the incoming organic substrate. |
format | Online Article Text |
id | pubmed-5947516 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-59475162018-06-01 Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes Lin, Che-Hung Pursley, Dominik Klein, Johannes E. M. N. Teske, Johannes Allen, Jennifer A. Rami, Fabian Köhn, Andreas Plietker, Bernd Chem Sci Chemistry The base metal complex Bu(4)N[Fe(CO)(3)(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the [Fe(CO)(3)(NO)] anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial π-complex with the incoming organic substrate. Royal Society of Chemistry 2015-12-01 2015-09-03 /pmc/articles/PMC5947516/ /pubmed/29861942 http://dx.doi.org/10.1039/c5sc02342d Text en This journal is © The Royal Society of Chemistry 2015 https://creativecommons.org/licenses/by/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) |
spellingShingle | Chemistry Lin, Che-Hung Pursley, Dominik Klein, Johannes E. M. N. Teske, Johannes Allen, Jennifer A. Rami, Fabian Köhn, Andreas Plietker, Bernd Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes |
title | Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
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title_full | Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
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title_fullStr | Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
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title_full_unstemmed | Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
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title_short | Non-decarbonylative photochemical versus thermal activation of Bu(4)N[Fe(CO)(3)(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
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title_sort | non-decarbonylative photochemical versus thermal activation of bu(4)n[fe(co)(3)(no)] – the fe-catalyzed cloke–wilson rearrangement of vinyl and arylcyclopropanes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5947516/ https://www.ncbi.nlm.nih.gov/pubmed/29861942 http://dx.doi.org/10.1039/c5sc02342d |
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