Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides

Kinetico-mechanistic studies on the substitution reactivity of the [Co{(μ-ET)cyclen}(H2O)2] 3+ complex cation at pH values within the 6.0-7.0 range with biologically significant ligands have been carried out. The substitution processes have been found to occur exclusively on the mono-hydroxobridged...

Descripción completa

Detalles Bibliográficos
Autores: Vázquez Valero, Marta, Font Bardia, Ma. Mercedes, Martínez López, Manuel, 1957-
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/164927
Acceso en línea:https://hdl.handle.net/2445/164927
Access Level:acceso abierto
Palabra clave:Cinètica química
Química bioinorgànica
Reaccions de substitució
Chemical kinetics
Bioinorganic chemistry
Substitution reactions
id ES_fcd82425c1cf5a811f475b4f775d2ed0
oai_identifier_str oai:recercat.cat:2445/164927
network_acronym_str ES
network_name_str España
repository_id_str
spelling Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotidesVázquez Valero, MartaFont Bardia, Ma. MercedesMartínez López, Manuel, 1957-Cinètica químicaQuímica bioinorgànicaReaccions de substitucióChemical kineticsBioinorganic chemistrySubstitution reactionsKinetico-mechanistic studies on the substitution reactivity of the [Co{(μ-ET)cyclen}(H2O)2] 3+ complex cation at pH values within the 6.0-7.0 range with biologically significant ligands have been carried out. The substitution processes have been found to occur exclusively on the mono-hydroxobridged [(Co{(μ-ET)cyclen}(H2O))2(μ-OH)]5+ species formed after equilibration of the cobalt complex in the relevant medium. The studies conducted on the substitution of the aqua/hydroxo ligands of this dinuclear species are indicative of a dominant role of outer-sphere complexation, involving hydrogen-bonding interactions. The values of the outer-sphere complex formation equilibrium constant are in line with the intervention of both the exiting aqua ligands and the NH groups at the encapsulating {(μ-ET)cyclen} ligand. These complexes result in the preferential formation of O- or N-bonded nucleotides depending on the structure of the base moiety of the ligand. Even the entry of the different donor bonded nucleotides is hampered by the hydrogen-bonding interaction with the dangling moiety of an already coordinated ligand. In general the overall substitution processes occur at a faster rate than those published for the fully alkylated encapsulating {(Me)2(μ-ET)cyclen} ligand derivative, as expected for the still available base-catalysing NH groups in the {(μ-ET)cyclen} ligand.Royal Society of Chemistry2020202020152020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion30 p.application/pdfhttps://hdl.handle.net/2445/164927Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1039/C5DT01816ADalton Transactions, 2015, vol. 44, num. 42, p. 18643-18655https://doi.org/10.1039/C5DT01816A(c) Vázquez Valero, Marta et al., 2015info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1649272026-05-29T05:05:01Z
dc.title.none.fl_str_mv Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
title Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
spellingShingle Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
Vázquez Valero, Marta
Cinètica química
Química bioinorgànica
Reaccions de substitució
Chemical kinetics
Bioinorganic chemistry
Substitution reactions
title_short Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
title_full Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
title_fullStr Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
title_full_unstemmed Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
title_sort Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides
dc.creator.none.fl_str_mv Vázquez Valero, Marta
Font Bardia, Ma. Mercedes
Martínez López, Manuel, 1957-
author Vázquez Valero, Marta
author_facet Vázquez Valero, Marta
Font Bardia, Ma. Mercedes
Martínez López, Manuel, 1957-
author_role author
author2 Font Bardia, Ma. Mercedes
Martínez López, Manuel, 1957-
author2_role author
author
dc.subject.none.fl_str_mv Cinètica química
Química bioinorgànica
Reaccions de substitució
Chemical kinetics
Bioinorganic chemistry
Substitution reactions
topic Cinètica química
Química bioinorgànica
Reaccions de substitució
Chemical kinetics
Bioinorganic chemistry
Substitution reactions
description Kinetico-mechanistic studies on the substitution reactivity of the [Co{(μ-ET)cyclen}(H2O)2] 3+ complex cation at pH values within the 6.0-7.0 range with biologically significant ligands have been carried out. The substitution processes have been found to occur exclusively on the mono-hydroxobridged [(Co{(μ-ET)cyclen}(H2O))2(μ-OH)]5+ species formed after equilibration of the cobalt complex in the relevant medium. The studies conducted on the substitution of the aqua/hydroxo ligands of this dinuclear species are indicative of a dominant role of outer-sphere complexation, involving hydrogen-bonding interactions. The values of the outer-sphere complex formation equilibrium constant are in line with the intervention of both the exiting aqua ligands and the NH groups at the encapsulating {(μ-ET)cyclen} ligand. These complexes result in the preferential formation of O- or N-bonded nucleotides depending on the structure of the base moiety of the ligand. Even the entry of the different donor bonded nucleotides is hampered by the hydrogen-bonding interaction with the dangling moiety of an already coordinated ligand. In general the overall substitution processes occur at a faster rate than those published for the fully alkylated encapsulating {(Me)2(μ-ET)cyclen} ligand derivative, as expected for the still available base-catalysing NH groups in the {(μ-ET)cyclen} ligand.
publishDate 2015
dc.date.none.fl_str_mv 2015
2020
2020
2020
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/2445/164927
url https://hdl.handle.net/2445/164927
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/10.1039/C5DT01816A
Dalton Transactions, 2015, vol. 44, num. 42, p. 18643-18655
https://doi.org/10.1039/C5DT01816A
dc.rights.none.fl_str_mv (c) Vázquez Valero, Marta et al., 2015
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Vázquez Valero, Marta et al., 2015
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 30 p.
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869425486303592448
score 15,81155

Similares en LA Referencia