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C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction

The C−X bond activation (X = H, C) of a series of substituted C(n°)−H and C(n°)−C(m°) bonds with C(n°) and C(m°) = H(3)C− (methyl, 0°), CH(3)H(2)C− (primary, 1°), (CH(3))(2)HC− (secondary, 2°), (CH(3))(3)C− (tertiary, 3°) by palladium were investigated using relativistic dispersion‐corrected density...

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Autores principales: Hansen, Thomas, Sun, Xiaobo, Dalla Tiezza, Marco, van Zeist, Willem‐Jan, van Stralen, Joost N. P., Geerke, Daan P., Wolters, Lando P., Poater, Jordi, Hamlin, Trevor A., Bickelhaupt, F. Matthias
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401605/
https://www.ncbi.nlm.nih.gov/pubmed/35420229
http://dx.doi.org/10.1002/chem.202201093
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author Hansen, Thomas
Sun, Xiaobo
Dalla Tiezza, Marco
van Zeist, Willem‐Jan
van Stralen, Joost N. P.
Geerke, Daan P.
Wolters, Lando P.
Poater, Jordi
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
author_facet Hansen, Thomas
Sun, Xiaobo
Dalla Tiezza, Marco
van Zeist, Willem‐Jan
van Stralen, Joost N. P.
Geerke, Daan P.
Wolters, Lando P.
Poater, Jordi
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
author_sort Hansen, Thomas
collection PubMed
description The C−X bond activation (X = H, C) of a series of substituted C(n°)−H and C(n°)−C(m°) bonds with C(n°) and C(m°) = H(3)C− (methyl, 0°), CH(3)H(2)C− (primary, 1°), (CH(3))(2)HC− (secondary, 2°), (CH(3))(3)C− (tertiary, 3°) by palladium were investigated using relativistic dispersion‐corrected density functional theory at ZORA‐BLYP‐D3(BJ)/TZ2P. The effect of the stepwise introduction of substituents was pinpointed at the C−X bond on the bond activation process. The C(n°)−X bonds become substantially weaker going from C(0°)−X, to C(1°)−X, to C(2°)−X, to C(3°)−X because of the increasing steric repulsion between the C(n°)‐ and X‐group. Interestingly, this often does not lead to a lower barrier for the C(n°)−X bond activation. The C−H activation barrier, for example, decreases from C(0°)−X, to C(1°)−X, to C(2°)−X and then increases again for the very crowded C(3°)−X bond. For the more congested C−C bond, in contrast, the activation barrier always increases as the degree of substitution is increased. Our activation strain and matching energy decomposition analyses reveal that these differences in C−H and C−C bond activation can be traced back to the opposing interplay between steric repulsion across the C−X bond versus that between the catalyst and substrate.
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spelling pubmed-94016052022-08-26 C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction Hansen, Thomas Sun, Xiaobo Dalla Tiezza, Marco van Zeist, Willem‐Jan van Stralen, Joost N. P. Geerke, Daan P. Wolters, Lando P. Poater, Jordi Hamlin, Trevor A. Bickelhaupt, F. Matthias Chemistry Research Articles The C−X bond activation (X = H, C) of a series of substituted C(n°)−H and C(n°)−C(m°) bonds with C(n°) and C(m°) = H(3)C− (methyl, 0°), CH(3)H(2)C− (primary, 1°), (CH(3))(2)HC− (secondary, 2°), (CH(3))(3)C− (tertiary, 3°) by palladium were investigated using relativistic dispersion‐corrected density functional theory at ZORA‐BLYP‐D3(BJ)/TZ2P. The effect of the stepwise introduction of substituents was pinpointed at the C−X bond on the bond activation process. The C(n°)−X bonds become substantially weaker going from C(0°)−X, to C(1°)−X, to C(2°)−X, to C(3°)−X because of the increasing steric repulsion between the C(n°)‐ and X‐group. Interestingly, this often does not lead to a lower barrier for the C(n°)−X bond activation. The C−H activation barrier, for example, decreases from C(0°)−X, to C(1°)−X, to C(2°)−X and then increases again for the very crowded C(3°)−X bond. For the more congested C−C bond, in contrast, the activation barrier always increases as the degree of substitution is increased. Our activation strain and matching energy decomposition analyses reveal that these differences in C−H and C−C bond activation can be traced back to the opposing interplay between steric repulsion across the C−X bond versus that between the catalyst and substrate. John Wiley and Sons Inc. 2022-06-16 2022-08-04 /pmc/articles/PMC9401605/ /pubmed/35420229 http://dx.doi.org/10.1002/chem.202201093 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Hansen, Thomas
Sun, Xiaobo
Dalla Tiezza, Marco
van Zeist, Willem‐Jan
van Stralen, Joost N. P.
Geerke, Daan P.
Wolters, Lando P.
Poater, Jordi
Hamlin, Trevor A.
Bickelhaupt, F. Matthias
C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title_full C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title_fullStr C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title_full_unstemmed C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title_short C−X Bond Activation by Palladium: Steric Shielding versus Steric Attraction
title_sort c−x bond activation by palladium: steric shielding versus steric attraction
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401605/
https://www.ncbi.nlm.nih.gov/pubmed/35420229
http://dx.doi.org/10.1002/chem.202201093
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