Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design

The factors controlling the activation of σ-bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, the influence of both the nature of the group 13 element acting as Lewis acid as well as the cooperative action of the Lewis antag...

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Authors: González-Pinardo, Daniel, Krämer, Felix, Breher, Frank, Fernández López, Israel
Format: article
Publication Date:2024
Country:España
Institution:Universidad Complutense de Madrid (UCM)
Repository:Docta Complutense
Language:English
OAI Identifier:oai:docta.ucm.es:20.500.14352/106078
Online Access:https://hdl.handle.net/20.500.14352/106078
Access Level:Open access
Keyword:546
Aluminum
Hidden Frustrated Lewis Pairs
Phosphorus ylides
Bond activation
DFT calculations
Química orgánica (Química)
2306 Química Orgánica
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oai_identifier_str oai:docta.ucm.es:20.500.14352/106078
network_acronym_str ES
network_name_str España
repository_id_str
spelling Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and DesignGonzález-Pinardo, DanielKrämer, FelixBreher, FrankFernández López, Israel546AluminumHidden Frustrated Lewis PairsPhosphorus ylidesBond activationDFT calculationsQuímica orgánica (Química)2306 Química OrgánicaThe factors controlling the activation of σ-bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, the influence of both the nature of the group 13 element acting as Lewis acid as well as the cooperative action of the Lewis antagonists on the bond activation was quantitatively analyzed by means of the activation strain model of reactivity in combination with the energy decomposition analysis method. It is found that while the activation of the polar EX−H bonds (E15=group 15 element; E16=group 16 element) is feasible, the analogous processes involving non-polar E14−H bonds (CH4, SiH4 or H2) proceed with much higher barriers. Nevertheless, these processes, and in particular the dihydrogen activation, can be realizable (i. e. proceeding with a feasible barrier) through rational design.WileyUniversidad Complutense de Madrid20242024-06-1720242024-06-17journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/106078reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)InglésengMICIU AEI 10.13039 PID2022-139318NB-I00MICIU AEI 10.13039 RED2022-134331-Topen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1060782026-06-02T12:44:21Z
dc.title.none.fl_str_mv Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
title Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
spellingShingle Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
González-Pinardo, Daniel
546
Aluminum
Hidden Frustrated Lewis Pairs
Phosphorus ylides
Bond activation
DFT calculations
Química orgánica (Química)
2306 Química Orgánica
title_short Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
title_full Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
title_fullStr Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
title_full_unstemmed Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
title_sort Activation of σ-Bonds by Group 13/Ylide-Based Ambiphiles: Understanding and Design
dc.creator.none.fl_str_mv González-Pinardo, Daniel
Krämer, Felix
Breher, Frank
Fernández López, Israel
author González-Pinardo, Daniel
author_facet González-Pinardo, Daniel
Krämer, Felix
Breher, Frank
Fernández López, Israel
author_role author
author2 Krämer, Felix
Breher, Frank
Fernández López, Israel
author2_role author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 546
Aluminum
Hidden Frustrated Lewis Pairs
Phosphorus ylides
Bond activation
DFT calculations
Química orgánica (Química)
2306 Química Orgánica
topic 546
Aluminum
Hidden Frustrated Lewis Pairs
Phosphorus ylides
Bond activation
DFT calculations
Química orgánica (Química)
2306 Química Orgánica
description The factors controlling the activation of σ-bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, the influence of both the nature of the group 13 element acting as Lewis acid as well as the cooperative action of the Lewis antagonists on the bond activation was quantitatively analyzed by means of the activation strain model of reactivity in combination with the energy decomposition analysis method. It is found that while the activation of the polar EX−H bonds (E15=group 15 element; E16=group 16 element) is feasible, the analogous processes involving non-polar E14−H bonds (CH4, SiH4 or H2) proceed with much higher barriers. Nevertheless, these processes, and in particular the dihydrogen activation, can be realizable (i. e. proceeding with a feasible barrier) through rational design.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-06-17
2024
2024-06-17
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/106078
url https://hdl.handle.net/20.500.14352/106078
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv MICIU AEI 10.13039 PID2022-139318NB-I00
MICIU AEI 10.13039 RED2022-134331-T
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812429

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