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Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures
Photochemical reactions in solution often proceed via competing reaction pathways comprising intermediates that capture a solvent molecule. A disclosure of the underlying reaction mechanisms is challenging due to the rapid nature of these processes and the intricate identification of how many solven...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5059701/ https://www.ncbi.nlm.nih.gov/pubmed/27708264 http://dx.doi.org/10.1038/ncomms12968 |
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author | Knorr, Johannes Sokkar, Pandian Schott, Sebastian Costa, Paolo Thiel, Walter Sander, Wolfram Sanchez-Garcia, Elsa Nuernberger, Patrick |
author_facet | Knorr, Johannes Sokkar, Pandian Schott, Sebastian Costa, Paolo Thiel, Walter Sander, Wolfram Sanchez-Garcia, Elsa Nuernberger, Patrick |
author_sort | Knorr, Johannes |
collection | PubMed |
description | Photochemical reactions in solution often proceed via competing reaction pathways comprising intermediates that capture a solvent molecule. A disclosure of the underlying reaction mechanisms is challenging due to the rapid nature of these processes and the intricate identification of how many solvent molecules are involved. Here combining broadband femtosecond transient absorption and quantum mechanics/molecular mechanics simulations, we show for one of the most reactive species, diphenylcarbene, that the decision-maker is not the nearest solvent molecule but its neighbour. The hydrogen bonding dynamics determine which reaction channels are accessible in binary solvent mixtures at room temperature. In-depth analysis of the amount of nascent intermediates corroborates the importance of a hydrogen-bonded complex with a protic solvent molecule, in striking analogy to complexes found at cryogenic temperatures. Our results show that adjacent solvent molecules take the role of key abettors rather than bystanders for the fate of the reactive intermediate. |
format | Online Article Text |
id | pubmed-5059701 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Nature Publishing Group |
record_format | MEDLINE/PubMed |
spelling | pubmed-50597012016-10-26 Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures Knorr, Johannes Sokkar, Pandian Schott, Sebastian Costa, Paolo Thiel, Walter Sander, Wolfram Sanchez-Garcia, Elsa Nuernberger, Patrick Nat Commun Article Photochemical reactions in solution often proceed via competing reaction pathways comprising intermediates that capture a solvent molecule. A disclosure of the underlying reaction mechanisms is challenging due to the rapid nature of these processes and the intricate identification of how many solvent molecules are involved. Here combining broadband femtosecond transient absorption and quantum mechanics/molecular mechanics simulations, we show for one of the most reactive species, diphenylcarbene, that the decision-maker is not the nearest solvent molecule but its neighbour. The hydrogen bonding dynamics determine which reaction channels are accessible in binary solvent mixtures at room temperature. In-depth analysis of the amount of nascent intermediates corroborates the importance of a hydrogen-bonded complex with a protic solvent molecule, in striking analogy to complexes found at cryogenic temperatures. Our results show that adjacent solvent molecules take the role of key abettors rather than bystanders for the fate of the reactive intermediate. Nature Publishing Group 2016-10-06 /pmc/articles/PMC5059701/ /pubmed/27708264 http://dx.doi.org/10.1038/ncomms12968 Text en Copyright © 2016, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Article Knorr, Johannes Sokkar, Pandian Schott, Sebastian Costa, Paolo Thiel, Walter Sander, Wolfram Sanchez-Garcia, Elsa Nuernberger, Patrick Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title | Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title_full | Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title_fullStr | Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title_full_unstemmed | Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title_short | Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
title_sort | competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5059701/ https://www.ncbi.nlm.nih.gov/pubmed/27708264 http://dx.doi.org/10.1038/ncomms12968 |
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