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cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms

Proton‐coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models...

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Detalles Bibliográficos
Autores principales: Klein, Johannes E. M. N., Knizia, Gerald
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6175160/
https://www.ncbi.nlm.nih.gov/pubmed/30019800
http://dx.doi.org/10.1002/anie.201805511
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author Klein, Johannes E. M. N.
Knizia, Gerald
author_facet Klein, Johannes E. M. N.
Knizia, Gerald
author_sort Klein, Johannes E. M. N.
collection PubMed
description Proton‐coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models of various complexity, it is now argued that it is both feasible and fruitful to directly analyze the electronic N‐electron wavefunctions of these processes along their intrinsic reaction coordinate (IRC). In particular, for model systems of lipoxygenase and the high‐valent oxoiron(IV) intermediate TauD‐J it is shown that by invoking the intrinsic bond orbital (IBO) representation of the wavefunction, the common boundary cases of hydrogen atom transfer (HAT) and concerted PCET (cPCET) can be directly and unambiguously distinguished in a straightforward manner.
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spelling pubmed-61751602018-10-15 cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms Klein, Johannes E. M. N. Knizia, Gerald Angew Chem Int Ed Engl Communications Proton‐coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models of various complexity, it is now argued that it is both feasible and fruitful to directly analyze the electronic N‐electron wavefunctions of these processes along their intrinsic reaction coordinate (IRC). In particular, for model systems of lipoxygenase and the high‐valent oxoiron(IV) intermediate TauD‐J it is shown that by invoking the intrinsic bond orbital (IBO) representation of the wavefunction, the common boundary cases of hydrogen atom transfer (HAT) and concerted PCET (cPCET) can be directly and unambiguously distinguished in a straightforward manner. John Wiley and Sons Inc. 2018-08-29 2018-09-10 /pmc/articles/PMC6175160/ /pubmed/30019800 http://dx.doi.org/10.1002/anie.201805511 Text en © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Klein, Johannes E. M. N.
Knizia, Gerald
cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title_full cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title_fullStr cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title_full_unstemmed cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title_short cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
title_sort cpcet versus hat: a direct theoretical method for distinguishing x–h bond‐activation mechanisms
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6175160/
https://www.ncbi.nlm.nih.gov/pubmed/30019800
http://dx.doi.org/10.1002/anie.201805511
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