Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence
Abstract 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 mode...
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crwiley:10.1002/chem.202100755 2024-09-15T18:01:37+00:00 Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence Garay‐Ruiz, Diego Bo, Carles Agència de Gestió d'Ajuts Universitaris i de Recerca Ministerio de Ciencia, Innovación y Universidades 2021 http://dx.doi.org/10.1002/chem.202100755 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202100755 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202100755 en eng Wiley http://creativecommons.org/licenses/by-nc/4.0/ Chemistry – A European Journal volume 27, issue 45, page 11618-11626 ISSN 0947-6539 1521-3765 journal-article 2021 crwiley https://doi.org/10.1002/chem.202100755 2024-08-09T04:30:00Z Abstract 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. Article in Journal/Newspaper Carbonic acid Wiley Online Library Chemistry – A European Journal 27 45 11618 11626 |
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Wiley Online Library |
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language |
English |
description |
Abstract 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. |
author2 |
Agència de Gestió d'Ajuts Universitaris i de Recerca Ministerio de Ciencia, Innovación y Universidades |
format |
Article in Journal/Newspaper |
author |
Garay‐Ruiz, Diego Bo, Carles |
spellingShingle |
Garay‐Ruiz, Diego Bo, Carles Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence |
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 |
Wiley |
publishDate |
2021 |
url |
http://dx.doi.org/10.1002/chem.202100755 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202100755 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202100755 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Chemistry – A European Journal volume 27, issue 45, page 11618-11626 ISSN 0947-6539 1521-3765 |
op_rights |
http://creativecommons.org/licenses/by-nc/4.0/ |
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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1810438732618137600 |