Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media

The C–Br and C–Cl oxidative addition reactions of molecules containing a set of {N-amino,N-imino} chelating donor groups (2-X,6-YC6H4CHNCH2CH2NMe2, X = Br, Cl; Y = Cl, H) attached to a {PtII(Ar)2} (Ar = Ph, 4-MeC6H4) have been studied. The Pt(IV) complexes formed, [PtAr2X{2-YCC5H3CH═NCH2CH2NMe2}], c...

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Detalles Bibliográficos
Autores: Calvet Pallàs, Maria Teresa, Crespo Vicente, Margarita Ma., Font Bardia, Ma. Mercedes, Jansat, Sussana, Martínez López, Manuel, 1957-
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2012
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/210360
Acceso en línea:https://hdl.handle.net/2445/210360
Access Level:acceso abierto
Palabra clave:Hidrocarburs
Lligands
Estructura molecular
Dissolvents
Hydrocarbons
Ligands
Molecular structure
Solvents
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spelling Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid mediaCalvet Pallàs, Maria TeresaCrespo Vicente, Margarita Ma.Font Bardia, Ma. MercedesJansat, SussanaMartínez López, Manuel, 1957-HidrocarbursLligandsEstructura molecularDissolventsHydrocarbonsLigandsMolecular structureSolventsThe C–Br and C–Cl oxidative addition reactions of molecules containing a set of {N-amino,N-imino} chelating donor groups (2-X,6-YC6H4CHNCH2CH2NMe2, X = Br, Cl; Y = Cl, H) attached to a {PtII(Ar)2} (Ar = Ph, 4-MeC6H4) have been studied. The Pt(IV) complexes formed, [PtAr2X{2-YCC5H3CH═NCH2CH2NMe2}], containing a metalated tridentate [C,N,N′] ligand have been fully characterized by the usual techniques, and the X-ray crystal structure of the complex with Ar = 4-MeC6H4 and X =Y = Cl has been determined. Monitoring of the reactions at varying temperatures and pressures and in different solvents agrees with a mechanism that involves the preliminary decoordination of the N-amino donor from the ligand to produce a three-coordinated intermediate. This evolves, via a concerted C–X bond activation, to form a second pentacoordinated intermediate species that, on coordination of the N-amino donor, produces the final complex. The kinetico-mechanistic parameters measured indicate that the concerted character of the process is maintained from nonpolar (xylene and toluene) to polar (acetone) and ionic liquid ((Bmin(NTf2)) media. Furthermore, the ΔV⧧ values measured indicate that, for the (2,6-Cl)C6H3CH═NCH2CH2NMe2 ligand, the existence of hydrogen bonding within the metalating molecule is a determinant for the acceleration observed.American Chemical Society2012info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/210360Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1021/om300374fOrganometallics, 2012, vol. 31, num.11, p. 4367-4373https://doi.org/10.1021/om300374f(c) American Chemical Society, 2012info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/2103602026-05-27T06:46:51Z
dc.title.none.fl_str_mv Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
title Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
spellingShingle Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
Calvet Pallàs, Maria Teresa
Hidrocarburs
Lligands
Estructura molecular
Dissolvents
Hydrocarbons
Ligands
Molecular structure
Solvents
title_short Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
title_full Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
title_fullStr Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
title_full_unstemmed Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
title_sort Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media
dc.creator.none.fl_str_mv Calvet Pallàs, Maria Teresa
Crespo Vicente, Margarita Ma.
Font Bardia, Ma. Mercedes
Jansat, Sussana
Martínez López, Manuel, 1957-
author Calvet Pallàs, Maria Teresa
author_facet Calvet Pallàs, Maria Teresa
Crespo Vicente, Margarita Ma.
Font Bardia, Ma. Mercedes
Jansat, Sussana
Martínez López, Manuel, 1957-
author_role author
author2 Crespo Vicente, Margarita Ma.
Font Bardia, Ma. Mercedes
Jansat, Sussana
Martínez López, Manuel, 1957-
author2_role author
author
author
author
dc.subject.none.fl_str_mv Hidrocarburs
Lligands
Estructura molecular
Dissolvents
Hydrocarbons
Ligands
Molecular structure
Solvents
topic Hidrocarburs
Lligands
Estructura molecular
Dissolvents
Hydrocarbons
Ligands
Molecular structure
Solvents
description The C–Br and C–Cl oxidative addition reactions of molecules containing a set of {N-amino,N-imino} chelating donor groups (2-X,6-YC6H4CHNCH2CH2NMe2, X = Br, Cl; Y = Cl, H) attached to a {PtII(Ar)2} (Ar = Ph, 4-MeC6H4) have been studied. The Pt(IV) complexes formed, [PtAr2X{2-YCC5H3CH═NCH2CH2NMe2}], containing a metalated tridentate [C,N,N′] ligand have been fully characterized by the usual techniques, and the X-ray crystal structure of the complex with Ar = 4-MeC6H4 and X =Y = Cl has been determined. Monitoring of the reactions at varying temperatures and pressures and in different solvents agrees with a mechanism that involves the preliminary decoordination of the N-amino donor from the ligand to produce a three-coordinated intermediate. This evolves, via a concerted C–X bond activation, to form a second pentacoordinated intermediate species that, on coordination of the N-amino donor, produces the final complex. The kinetico-mechanistic parameters measured indicate that the concerted character of the process is maintained from nonpolar (xylene and toluene) to polar (acetone) and ionic liquid ((Bmin(NTf2)) media. Furthermore, the ΔV⧧ values measured indicate that, for the (2,6-Cl)C6H3CH═NCH2CH2NMe2 ligand, the existence of hydrogen bonding within the metalating molecule is a determinant for the acceleration observed.
publishDate 2012
dc.date.none.fl_str_mv 2012
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/2445/210360
url https://hdl.handle.net/2445/210360
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/10.1021/om300374f
Organometallics, 2012, vol. 31, num.11, p. 4367-4373
https://doi.org/10.1021/om300374f
dc.rights.none.fl_str_mv (c) American Chemical Society, 2012
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society, 2012
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 15.301603

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