Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/164927
Title: | Kinetico-mechanistic studies on substitution reactions on cross-bridged cyclen CoIII complexes with nucleosides and nucleotides |
Author: | Vázquez Valero, Marta Font Bardia, Ma. Mercedes Martínez López, Manuel, 1957- |
Keywords: | Cinètica química Química bioinorgànica Reaccions de substitució Chemical kinetics Bioinorganic chemistry Substitution reactions |
Issue Date: | 2015 |
Publisher: | Royal Society of Chemistry |
Abstract: | 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. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1039/C5DT01816A |
It is part of: | Dalton Transactions, 2015, vol. 44, num. 42, p. 18643-18655 |
URI: | http://hdl.handle.net/2445/164927 |
Related resource: | https://doi.org/10.1039/C5DT01816A |
ISSN: | 1477-9226 |
Appears in Collections: | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
654792.pdf | 1.7 MB | Adobe PDF | View/Open |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.