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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...

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Autores principales: Knorr, Johannes, Sokkar, Pandian, Schott, Sebastian, Costa, Paolo, Thiel, Walter, Sander, Wolfram, Sanchez-Garcia, Elsa, Nuernberger, Patrick
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
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.
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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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