Kinetic studies on H+- and OH−-catalysed aquation of bis-aspartatochromium(III)

A potential synthetic biochromium source, bis-aspartatochromium(III) ion (where Asp is a tridentate N,O,O′-ligand, bonded via amine nitrogen and carboxylate oxygen atoms) has been obtained and characterized in aqueous solution. Kinetics of partial dechelation of the complex catalysed by H + and OH −...

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Bibliographic Details
Published in:Transition metal chemistry (Weinheim) 2014-02, Vol.39 (1), p.63-70
Main Authors: Kita, Ewa, Kiersikowska, Emilia, Marai, Hasan, Mierkiewicz, Karolina
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Chemistry and Materials Science
Inorganic Chemistry
Organometallic Chemistry
Physical Chemistry
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Summary:A potential synthetic biochromium source, bis-aspartatochromium(III) ion (where Asp is a tridentate N,O,O′-ligand, bonded via amine nitrogen and carboxylate oxygen atoms) has been obtained and characterized in aqueous solution. Kinetics of partial dechelation of the complex catalysed by H + and OH − ions has been studied spectrophotometrically within 0.1–1.0 M HClO 4 and 0.1–1.0 M NaOH ranges under first-order conditions. A linear dependence of the k obs,H on [H + ] and independence of the k obs,OH on [OH − ] were established. The derived rate expression and identification of components of the reaction mixture provide evidence for a reaction mechanism, where the key role in the overall process is the formation of an intermediate species with bidentate N,O-bonded Asp via both spontaneous and H + (OH − )-catalysed reaction paths. The intermediate is meta-stable and at pH 5–7 restores the substrate.
ISSN:0340-4285
1572-901X
DOI:10.1007/s11243-013-9775-8