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Cyclo[18]carbon Formation from C(18)Br(6) and C(18)(CO)(6) Precursors
[Image: see text] Although cyclo[18]carbon has been isolated experimentally from two precursors, C(18)Br(6) and C(18)(CO)(6), no reaction mechanisms have yet been explored. Herein, we provide insight into the mechanism behind debromination and decarbonylation. Both neutral precursors demonstrate hig...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9661529/ https://www.ncbi.nlm.nih.gov/pubmed/36306526 http://dx.doi.org/10.1021/acs.jpclett.2c02659 |
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author | Suresh, Rahul Baryshnikov, Glib V. Kuklin, Artem V. Nemkova, Diana I. Saikova, Svetlana V. Ågren, Hans |
author_facet | Suresh, Rahul Baryshnikov, Glib V. Kuklin, Artem V. Nemkova, Diana I. Saikova, Svetlana V. Ågren, Hans |
author_sort | Suresh, Rahul |
collection | PubMed |
description | [Image: see text] Although cyclo[18]carbon has been isolated experimentally from two precursors, C(18)Br(6) and C(18)(CO)(6), no reaction mechanisms have yet been explored. Herein, we provide insight into the mechanism behind debromination and decarbonylation. Both neutral precursors demonstrate high activation barriers of ∼2.3 eV, while the application of an electric field can lower the barriers by 0.1–0.2 eV. The barrier energy of the anion-radicals is found to be significantly lower for C(18)Br(6) compared to C(18)(CO)(6), confirming a considerably higher yield of cylco[18]carbon when the C(18)Br(6) precursor is used. Elongation of the C–Br bond in the anion-radical confirms its predissociation condition. Natural bonding orbital analysis shows that the stability of C–Br and C–CO bonds in the anion-radicals is lower compared to their neutral species, indicating a possible higher yield. The applied analysis provides crucial details regarding the reaction yield of cyclo[18]carbon and can serve as a general scheme for tuning reaction conditions for other organic precursors. |
format | Online Article Text |
id | pubmed-9661529 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-96615292022-11-15 Cyclo[18]carbon Formation from C(18)Br(6) and C(18)(CO)(6) Precursors Suresh, Rahul Baryshnikov, Glib V. Kuklin, Artem V. Nemkova, Diana I. Saikova, Svetlana V. Ågren, Hans J Phys Chem Lett [Image: see text] Although cyclo[18]carbon has been isolated experimentally from two precursors, C(18)Br(6) and C(18)(CO)(6), no reaction mechanisms have yet been explored. Herein, we provide insight into the mechanism behind debromination and decarbonylation. Both neutral precursors demonstrate high activation barriers of ∼2.3 eV, while the application of an electric field can lower the barriers by 0.1–0.2 eV. The barrier energy of the anion-radicals is found to be significantly lower for C(18)Br(6) compared to C(18)(CO)(6), confirming a considerably higher yield of cylco[18]carbon when the C(18)Br(6) precursor is used. Elongation of the C–Br bond in the anion-radical confirms its predissociation condition. Natural bonding orbital analysis shows that the stability of C–Br and C–CO bonds in the anion-radicals is lower compared to their neutral species, indicating a possible higher yield. The applied analysis provides crucial details regarding the reaction yield of cyclo[18]carbon and can serve as a general scheme for tuning reaction conditions for other organic precursors. American Chemical Society 2022-10-28 2022-11-10 /pmc/articles/PMC9661529/ /pubmed/36306526 http://dx.doi.org/10.1021/acs.jpclett.2c02659 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Suresh, Rahul Baryshnikov, Glib V. Kuklin, Artem V. Nemkova, Diana I. Saikova, Svetlana V. Ågren, Hans Cyclo[18]carbon Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title | Cyclo[18]carbon
Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title_full | Cyclo[18]carbon
Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title_fullStr | Cyclo[18]carbon
Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title_full_unstemmed | Cyclo[18]carbon
Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title_short | Cyclo[18]carbon
Formation from C(18)Br(6) and C(18)(CO)(6) Precursors |
title_sort | cyclo[18]carbon
formation from c(18)br(6) and c(18)(co)(6) precursors |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9661529/ https://www.ncbi.nlm.nih.gov/pubmed/36306526 http://dx.doi.org/10.1021/acs.jpclett.2c02659 |
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