Kinetics and mechanism of the chromic oxidation of myo-inositol

The redox reaction of myo-inositol with Cr VI yields the inosose and Cr III as final redox products. The reaction occurs through a mechanism that combines Cr VI → Cr IV → Cr II and Cr VI → Cr IV → Cr III pathways. The oxidation of d- myo-inositol (Myo) by Cr VI yields the inosose and Cr 3+ as final...

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Bibliographic Details
Published in:Polyhedron 2007-01, Vol.26 (1), p.169-177
Main Authors: Santoro, Mabel, Caffaratti, Evangelina, Salas-Peregrin, Juan Manuel, Korecz, Laszlo, Rockenbauer, Antal, Sala, Luis F., Signorella, Sandra
Format: Article
Language:English
Subjects:
Chromate
Complexation chemistry
myo-Inositol
Redox chemistry
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Summary:The redox reaction of myo-inositol with Cr VI yields the inosose and Cr III as final redox products. The reaction occurs through a mechanism that combines Cr VI → Cr IV → Cr II and Cr VI → Cr IV → Cr III pathways. The oxidation of d- myo-inositol (Myo) by Cr VI yields the inosose and Cr 3+ as final products when an excess of cyclitol over Cr VI is used. The redox reaction takes place through the combination of Cr VI → Cr IV → Cr II and Cr VI → Cr IV → Cr III pathways. Intermediacy of Cr IV was evidenced by the detection of CrO 2 2 + , formed by reaction of Cr II with O 2. The EPR spectra show that five- and six-coordinated oxo-Cr V intermediates are formed, with the cyclitol acting as bidentate ligand. Penta-coordinated oxo-Cr V species are present at any [H +], whereas hexa-coordinated ones are only observed at pH < 1, where rapidly decompose to the redox products. At higher pH, where hexa-coordinated oxo-Cr V species are not observed, oxo-Cr V bischelates are stable enough to remain long time in solution.
ISSN:0277-5387
DOI:10.1016/j.poly.2006.08.003