Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study

Bernhardt, Paul V., Martínez, Manuel, Rodríguez, Carlos and Vazquez, Marta (2012) Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study. Dalton Transactions, 41 7: 2122-2130. doi:10.1039/C1DT11685A

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Author Bernhardt, Paul V.
Martínez, Manuel
Rodríguez, Carlos
Vazquez, Marta
Title Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
1477-9234
Publication date 2012
Year available 2011
Sub-type Article (original research)
DOI 10.1039/C1DT11685A
Open Access Status File (Publisher version)
Volume 41
Issue 7
Start page 2122
End page 2130
Total pages 9
Editor Jamie Humphrey
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Collection year 2012
Language eng
Formatted abstract
The FeIII abstraction from FeIII/DFO and FeIII/EDTA complex systems by thiosemicarbazone ligands derived from 2-acetylpyridine has been studied from a kinetico-mechanistic perspective at relevant pH conditions and at varying temperatures and buffer solutions. The reactions have been found to be extremely dependent on the dominant E/Z isomeric form of the TSC ligands present in the reaction medium. Consequently the isomerisation processes occurring on the free ligands have also been monitored under equivalent conditions. The isomerisation process is found to be acid dependent, despite the absence of protonation under the conditions used, and presumably proceeds via an azo-type tautomer of the ligand. In all cases the existence of outer-sphere interaction processes has been established, both promoting the reactions and producing dead-end complexes. The better oriented forms of the ligands (EZ thiolate) have been found to react faster with the [Fe(HDFO)]+ complex, although for mono-N4 substituted thiosemicarbazones the process is retarded by the formation of a dead-end outer-sphere complex. A comparison with the abstraction of FeIII from [Fe(EDTA)(H2O)]- has also been conducted with significant differences in the kinetic features that implicate keystone outer-sphere interactions which dominate reactivity, even with isomeric forms that are not the best suited for direct complexation.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes First published on the web 19 Dec 2011

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Wed, 21 Dec 2011, 09:39:25 EST by Lucy O'Brien on behalf of School of Chemistry & Molecular Biosciences