Comparative study of the catalytic behaviour of Ru(III) and Ru(VI) on the oxidation of alcohols by hexacyanoferrate(III)
Article first published online: 11 FEB 2004
Copyright © 2004 John Wiley & Sons, Ltd.
Journal of Physical Organic Chemistry
Volume 17, Issue 3, pages 236–240, March 2004
How to Cite
Mucientes, A. E., Gabaldón, R. E., Poblete, F. J. and Villarreal, S. (2004), Comparative study of the catalytic behaviour of Ru(III) and Ru(VI) on the oxidation of alcohols by hexacyanoferrate(III). J. Phys. Org. Chem., 17: 236–240. doi: 10.1002/poc.721
- Issue published online: 11 FEB 2004
- Article first published online: 11 FEB 2004
- Manuscript Accepted: 3 OCT 2003
- Manuscript Revised: 18 JUN 2003
- Manuscript Received: 17 MAR 2003
- Consejería de Educación y Cultura de la Junta de Comunidades de Castilla La Mancha
The oxidation reactions of 2-methyl-2,4-pentanediol upon treatment with alkaline hexacyanoferrate(III) using Ru(III) or Ru(VI) as catalysts are governed by two quasi-identical experimental rate equations, which show that both catalysts are equally effective for the oxidation of alcohols by . The reaction mechanism proposed involves the oxidation of 2-methyl-2,4-pentanediol by the catalyst, a process that occurs through the formation of a substrate–catalyst complex. The decomposition of this complex yields Ru(IV) and a protonated ketone (owing to a hydride transfer from the α-C—H bond of the alcohol to the oxoligand of ruthenium) in the case of Ru(VI), but a ketyl radical and Ru(II) (hydrogen transfer) for Ru(III). The role of the co-oxidant, , is to regenerate the catalyst. For both oxidation reactions, the rate constants of complex decomposition and catalyst regeneration have been determined. Copyright © 2004 John Wiley & Sons, Ltd.