Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence
The heterolytic decomposition of tert‐butyl peroxyformate to tert‐butanol and carbon dioxide, catalyzed by pyridine, is a long‐known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an exten...
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ftpubmed:oai:pubmedcentral.nih.gov:8457178 2023-05-15T15:52:36+02:00 Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence Garay‐Ruiz, Diego Bo, Carles 2021-06-26 http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457178/ http://www.ncbi.nlm.nih.gov/pubmed/34076322 https://doi.org/10.1002/chem.202100755 en eng John Wiley and Sons Inc. http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457178/ http://www.ncbi.nlm.nih.gov/pubmed/34076322 http://dx.doi.org/10.1002/chem.202100755 © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. CC-BY-NC Chemistry Full Papers Text 2021 ftpubmed https://doi.org/10.1002/chem.202100755 2021-10-03T00:45:03Z The heterolytic decomposition of tert‐butyl peroxyformate to tert‐butanol and carbon dioxide, catalyzed by pyridine, is a long‐known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine‐mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)‐def2‐TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth. Text Carbonic acid PubMed Central (PMC) Chemistry – A European Journal 27 45 11618 11626 |
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Full Papers Garay‐Ruiz, Diego Bo, Carles Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
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Full Papers |
description |
The heterolytic decomposition of tert‐butyl peroxyformate to tert‐butanol and carbon dioxide, catalyzed by pyridine, is a long‐known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine‐mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)‐def2‐TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth. |
format |
Text |
author |
Garay‐Ruiz, Diego Bo, Carles |
author_facet |
Garay‐Ruiz, Diego Bo, Carles |
author_sort |
Garay‐Ruiz, Diego |
title |
Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
title_short |
Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
title_full |
Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
title_fullStr |
Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
title_full_unstemmed |
Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
title_sort |
rationalizing the mechanism of peroxyformate decomposition: computational insights to understand solvent influence |
publisher |
John Wiley and Sons Inc. |
publishDate |
2021 |
url |
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457178/ http://www.ncbi.nlm.nih.gov/pubmed/34076322 https://doi.org/10.1002/chem.202100755 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Chemistry |
op_relation |
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457178/ http://www.ncbi.nlm.nih.gov/pubmed/34076322 http://dx.doi.org/10.1002/chem.202100755 |
op_rights |
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
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CC-BY-NC |
op_doi |
https://doi.org/10.1002/chem.202100755 |
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Chemistry – A European Journal |
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27 |
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45 |
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11618 |
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11626 |
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1766387734685941760 |