• español
    • English
  • Login
  • English 
    • español
    • English

UniversidaddeCádiz

Área de Biblioteca, Archivo y Publicaciones
Communities and Collections
View Item 
  •   RODIN Home
  • Institutos de Investigación
  • Instituto de Investigación en Biomoléculas INBIO
  • Artículos Científicos INBIO
  • View Item
  •   RODIN Home
  • Institutos de Investigación
  • Instituto de Investigación en Biomoléculas INBIO
  • Artículos Científicos INBIO
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Equilibrium and kinetics studies on bibrachial lariat aza-crown/Cu(II) systems reveal different behavior associated with small changes in the structure

Thumbnail
Identificadores

URI: http://hdl.handle.net/10498/20482

DOI: 10.1016/j.ica.2013.12.020

Files
2014-Equilibrium and kinetics studies on bibrachial lariat aza-crownCu(II) systems reveal different behavior associated with small changes in the structure.pdf (3.170Mb)
Statistics
View statistics
Metrics and citations
 
Share
Export
Export reference to MendeleyRefworksEndNoteBibTexRIS
Metadata
Show full item record
Author/s
Castillo González, Carmen Esther; García Algarra, Andrés; Ferrer, Armando; Máñez Muñoz, María Ángeles; García Basallote, Manuel; Clares, M. Paz; Soriano, Concepción; Albelda, M. Teresa; García España, Enrique
Date
2014
Department
Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
Source
Inorganica Chimica Acta 417 (2014) 246–257
Abstract
The high-yield synthesis of a new bibrachial lariat azacrown constituted by two tris(2-aminoethyl)amine (tren) units functionalized in one of its arms with a 4-methylquinoline group linked by dimethylene pyridine spacers (L2) is reported for the first time. The speciation studies show formation of mono- and binuclear Cu2+ complexes of similar stability. Comparisons are established with the complexes formed by the precursor tren-quinoline derivative (L4) and with the previously reported ligands containing naphthalene instead of quinoline as the fluorophore (L1, L3). The kinetics of formation and decomposition of Cu2+ complexes with L1 and L2 has been studied. For L1, the acid-promoted decomposition of mono and dinuclear complexes occurs in all cases with a rapid step within the stopped-flow mixing time that leads to the formation of an intermediate that decomposes in two additional steps. In the dinuclear complexes, both metal ions dissociate from the ligand with statistically-controlled kinetics. Complex formation with L1 occurs through the same intermediate observed during the decomposition. For L2, only the formation and decomposition of binuclear complexes could be studied, and the kinetic data show that the metal ion can coordinate both in square pyramidal sp and trigonal bipyramidal (tbp) geometries, coordination being faster in the sp environment and dissociation being faster from tbp. DFT and TD-DFT have been also carried out to determine the geometries with both coordination environments as well as their electronic spectra. The results of calculations indicate that the appearance or not of a mixture of coordination geometries does not necessarily require the participation of the quinoline ring.
Subjects
Azacrown; Macrocycle; Copper(II); Coordination geometry; Potentiometric equilibrium studies; Kinetics
Collections
  • Artículos Científicos [3208]
  • Articulos Científicos CC. Mat. [97]
  • Artículos Científicos INBIO [204]
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
This work is under a Creative Commons License Attribution-NonCommercial-NoDerivatives 4.0 Internacional

Browse

All of RODINCommunities and CollectionsBy Issue DateAuthorsTitlesSubjectsThis CollectionBy Issue DateAuthorsTitlesSubjects

My Account

LoginRegister

Statistics

View Usage Statistics

Información adicional

AboutDeposit in RODINPoliciesGuidelinesRightsLinksStatisticsNewsFrequently Asked Questions

RODIN is available through

OpenAIREOAIsterRecolectaHispanaEuropeanaBaseDARTOATDGoogle Academic

Related links

Sherpa/RomeoDulcineaROAROpenDOARCreative CommonsORCID

RODIN está gestionado por el Área de Biblioteca, Archivo y Publicaciones de la Universidad de Cádiz

Contact informationSuggestionsUser Support