The Fe-catalyzed oxidation of aroyl hydrazones to aroyl hydrazines: mechanistic insight to a remarkable reaction

Bernhardt, Paul V. and Martinez, Manuel (2010) The Fe-catalyzed oxidation of aroyl hydrazones to aroyl hydrazines: mechanistic insight to a remarkable reaction. Journal of Coordination Chemistry, 63 14-16: 2619-2628. doi:10.1080/00958972.2010.491912

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Author Bernhardt, Paul V.
Martinez, Manuel
Title The Fe-catalyzed oxidation of aroyl hydrazones to aroyl hydrazines: mechanistic insight to a remarkable reaction
Journal name Journal of Coordination Chemistry   Check publisher's open access policy
ISSN 0095-8972
Publication date 2010-07
Sub-type Article (original research)
DOI 10.1080/00958972.2010.491912
Volume 63
Issue 14-16
Start page 2619
End page 2628
Total pages 10
Place of publication Abingdon
Publisher Taylor & Francis
Collection year 2011
Language eng
Abstract The FeIII-catalyzed oxidation of pyridinecarbaldehyde isonicotinoyl hydrazone to isonicotinoyl picolinoyl hydrazine in aqueous solution has been studied from a kinetico-mechanistic perspective. The reaction is more complex than one would anticipate from the known simple and reproducible preparative procedures. A series of very fast ligand coordination reactions to the FeIII center are followed by slower-N=CH-bond hydrolysis and rapid ligand-to-metal electron transfer coupled to Ḣ elimination. These processes lead to a partially oxidized ligand mixture with FeII coordinated to unreacted hydrazone. The slow decomposition of this FeII-hydrazone complex in aerobic alkaline solution produces ferric hydroxide as a new source of FeIII to sustain the hydrazone (-CO-NH-N=CH-) to hydrazine (CO-NH-NH-CO-) oxidation. © 2010 Taylor & Francis.
Keyword Iron chelators
Mechanism
Hydrazone oxidation
Iron Overload Disorders
Oxygen-atom Transfer
Coordination Chemistry
Biological-activity
Complexes
Chelators
Ligands
Aldimine
Family
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2011 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Sun, 05 Sep 2010, 00:05:09 EST