Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]

Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMePh)], revealing the crucial role of an open-shell singlet transition state for halide abstraction. The formation of Ni I versus Ni II has been rationalised thro...

Full description

Bibliographic Details
Authors: Funes-Ardoiz, Ignacio|||0000-0002-5843-9660, Nelson, David J.|||0000-0002-9461-5182, Maseras Cuní, Feliu|||0000-0001-8806-2019
Format: article
Publication Date:2017
Country:España
Institution:Universitat Autònoma de Barcelona
Repository:Dipòsit Digital de Documents de la UAB
Language:English
OAI Identifier:oai:ddd.uab.cat:186358
Online Access:https://ddd.uab.cat/record/186358
https://dx.doi.org/urn:doi:10.1002/chem.201702331
Access Level:Open access
Keyword:Density functional calculations
Electron transfer
Homogeneous catalysis
Ligand effects
Nickel
id ES_43d021c005ff8a9f9862bc28644f8612
oai_identifier_str oai:ddd.uab.cat:186358
network_acronym_str ES
network_name_str España
repository_id_str
spelling Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]Funes-Ardoiz, Ignacio|||0000-0002-5843-9660Nelson, David J.|||0000-0002-9461-5182Maseras Cuní, Feliu|||0000-0001-8806-2019Density functional calculationsElectron transferHomogeneous catalysisLigand effectsNickelDensity functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMePh)], revealing the crucial role of an open-shell singlet transition state for halide abstraction. The formation of Ni I versus Ni II has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMePh)], via an open-shell singlet transition state; (ii) S2-type oxidative addition to [Ni(PMePh)], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMePh)]. For the overall reaction between [Ni(PMe)], PhCl, and PhI, a microkinetic model was used to show that our results are consistent with the experimentally observed ratios of Ni I and Ni II when the PEt complex is used. Importantly, [Ni(PMePh)] complexes often have little, if any, role in oxidative addition reactions because they are relatively high in energy. The behaviour of [Ni(PR)] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni 0 complexes are the key species undergoing oxidative addition. 22017-01-0120172017-01-01Articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/186358https://dx.doi.org/urn:doi:10.1002/chem.201702331reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengMinisterio de Economía y Competitividad https://doi.org/10.13039/501100003329 CTQ2014-57761-RMinisterio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2013-0319Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SVP-2014-068662open accesshttp://purl.org/coar/access_right/c_abf2Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:1863582026-06-06T12:50:31Z
dc.title.none.fl_str_mv Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
title Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
spellingShingle Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
Funes-Ardoiz, Ignacio|||0000-0002-5843-9660
Density functional calculations
Electron transfer
Homogeneous catalysis
Ligand effects
Nickel
title_short Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
title_full Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
title_fullStr Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
title_full_unstemmed Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
title_sort Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMePh)]
dc.creator.none.fl_str_mv Funes-Ardoiz, Ignacio|||0000-0002-5843-9660
Nelson, David J.|||0000-0002-9461-5182
Maseras Cuní, Feliu|||0000-0001-8806-2019
author Funes-Ardoiz, Ignacio|||0000-0002-5843-9660
author_facet Funes-Ardoiz, Ignacio|||0000-0002-5843-9660
Nelson, David J.|||0000-0002-9461-5182
Maseras Cuní, Feliu|||0000-0001-8806-2019
author_role author
author2 Nelson, David J.|||0000-0002-9461-5182
Maseras Cuní, Feliu|||0000-0001-8806-2019
author2_role author
author
dc.subject.none.fl_str_mv Density functional calculations
Electron transfer
Homogeneous catalysis
Ligand effects
Nickel
topic Density functional calculations
Electron transfer
Homogeneous catalysis
Ligand effects
Nickel
description Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMePh)], revealing the crucial role of an open-shell singlet transition state for halide abstraction. The formation of Ni I versus Ni II has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMePh)], via an open-shell singlet transition state; (ii) S2-type oxidative addition to [Ni(PMePh)], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMePh)]. For the overall reaction between [Ni(PMe)], PhCl, and PhI, a microkinetic model was used to show that our results are consistent with the experimentally observed ratios of Ni I and Ni II when the PEt complex is used. Importantly, [Ni(PMePh)] complexes often have little, if any, role in oxidative addition reactions because they are relatively high in energy. The behaviour of [Ni(PR)] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni 0 complexes are the key species undergoing oxidative addition.
publishDate 2017
dc.date.none.fl_str_mv 2
2017-01-01
2017
2017-01-01
dc.type.none.fl_str_mv 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://ddd.uab.cat/record/186358
https://dx.doi.org/urn:doi:10.1002/chem.201702331
url https://ddd.uab.cat/record/186358
https://dx.doi.org/urn:doi:10.1002/chem.201702331
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 CTQ2014-57761-R
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2013-0319
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SVP-2014-068662
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://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
https://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869407050089365504
score 15,301603

Similar Items