Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence

Oxidative addition and reductive elimination reactions are fundamental steps in processes related to synthetic chemistry involving organometallic compounds. In these reactions a metal in two available oxidation states (generally differing in two units) is needed, platinum centers being a very good e...

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Autores: Aullón López, Gabriel, Crespo Vicente, Margarita Ma., Jover Modrego, Jesús, Martínez López, Manuel, 1957-
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Recursos:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/142917
Acesso em linha:https://hdl.handle.net/2445/142917
Access Level:acceso abierto
Palavra-chave:Cinètica química
Estrès oxidatiu
Compostos organometàl·lics
Chemical kinetics
Oxidative stress
Organometallic compounds
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spelling Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition SequenceAullón López, GabrielCrespo Vicente, Margarita Ma.Jover Modrego, JesúsMartínez López, Manuel, 1957-Cinètica químicaEstrès oxidatiuCompostos organometàl·licsChemical kineticsOxidative stressOrganometallic compoundsOxidative addition and reductive elimination reactions are fundamental steps in processes related to synthetic chemistry involving organometallic compounds. In these reactions a metal in two available oxidation states (generally differing in two units) is needed, platinum centers being a very good example. The relative inertness of diamagnetic PtII and PtIV organometallic species (having, respectively, d8 square-planar or d6 octahedral arrangements), enables an easy monitoring of time-resolved reactivity, including its posterior kinetic analysis. Specifically, imine ligands containing C-X bonds have been observed to oxidatively add to {PtII(Aryl)2} moieties, which sequentially undergo C-C reductive elimination and C-H bond activation on the new ligand formed. These new species have been found to contain mostly seven-membered metallacycles, despite the obvious thermodynamic preference for five-membered cycles, which are found only in some rather specific instances. The kinetic preference of the complexes obtained has been studied from a kinetico-mechanistic perspective, that included obtaining thermal- and pressure-derived activation parameters, and a dramatic influence on the spectator halido ligands, and the substituents on the aryl groups has been established. To complete this kinetic and mechanism (kinetico-mechanistic) study, theoretical calculations have also been conducted to model the data collected and propose both the elementary steps and the factors determining the specificity of the full process.Elsevier2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/142917Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1016/bs.adioch.2017.01.001Advances in Inorganic Chemistry, 2017, vol. 70, p. 195-242https://doi.org/10.1016/bs.adioch.2017.01.001(c) Elsevier, 2017info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1429172026-05-27T06:46:51Z
dc.title.none.fl_str_mv Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
title Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
spellingShingle Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
Aullón López, Gabriel
Cinètica química
Estrès oxidatiu
Compostos organometàl·lics
Chemical kinetics
Oxidative stress
Organometallic compounds
title_short Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
title_full Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
title_fullStr Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
title_full_unstemmed Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
title_sort Diarylplatinum(II) Scaffolds for Kinetic and Mechanistic Studies on the Formation of Platinacycles via an Oxidative Addition/Reductive Elimination/Oxidative Addition Sequence
dc.creator.none.fl_str_mv Aullón López, Gabriel
Crespo Vicente, Margarita Ma.
Jover Modrego, Jesús
Martínez López, Manuel, 1957-
author Aullón López, Gabriel
author_facet Aullón López, Gabriel
Crespo Vicente, Margarita Ma.
Jover Modrego, Jesús
Martínez López, Manuel, 1957-
author_role author
author2 Crespo Vicente, Margarita Ma.
Jover Modrego, Jesús
Martínez López, Manuel, 1957-
author2_role author
author
author
dc.subject.none.fl_str_mv Cinètica química
Estrès oxidatiu
Compostos organometàl·lics
Chemical kinetics
Oxidative stress
Organometallic compounds
topic Cinètica química
Estrès oxidatiu
Compostos organometàl·lics
Chemical kinetics
Oxidative stress
Organometallic compounds
description Oxidative addition and reductive elimination reactions are fundamental steps in processes related to synthetic chemistry involving organometallic compounds. In these reactions a metal in two available oxidation states (generally differing in two units) is needed, platinum centers being a very good example. The relative inertness of diamagnetic PtII and PtIV organometallic species (having, respectively, d8 square-planar or d6 octahedral arrangements), enables an easy monitoring of time-resolved reactivity, including its posterior kinetic analysis. Specifically, imine ligands containing C-X bonds have been observed to oxidatively add to {PtII(Aryl)2} moieties, which sequentially undergo C-C reductive elimination and C-H bond activation on the new ligand formed. These new species have been found to contain mostly seven-membered metallacycles, despite the obvious thermodynamic preference for five-membered cycles, which are found only in some rather specific instances. The kinetic preference of the complexes obtained has been studied from a kinetico-mechanistic perspective, that included obtaining thermal- and pressure-derived activation parameters, and a dramatic influence on the spectator halido ligands, and the substituents on the aryl groups has been established. To complete this kinetic and mechanism (kinetico-mechanistic) study, theoretical calculations have also been conducted to model the data collected and propose both the elementary steps and the factors determining the specificity of the full process.
publishDate 2017
dc.date.none.fl_str_mv 2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/142917
url https://hdl.handle.net/2445/142917
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1016/bs.adioch.2017.01.001
Advances in Inorganic Chemistry, 2017, vol. 70, p. 195-242
https://doi.org/10.1016/bs.adioch.2017.01.001
dc.rights.none.fl_str_mv (c) Elsevier, 2017
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Elsevier, 2017
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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