Kinetics and mechanism of uncatalysed and ruthenium(III) catalysed oxidation of allyl alcohol by diperiodatoargentate(III) in aqueous alkaline medium

摘要: The oxidation of allyl alcohol by diperiodatoargentate(III) (DPA) is carried out both in the absence and presence ruthenium(III) catalyst alkaline medium at 298 K a constant ionic strength 1.1 mol dm−3 was studied spectrophotometrically. products cases were acrolein Ag(I), identified spectral studies. stoichiometry same cases, that is, [AA]/[DPA] = 1:1. reaction shows first order [DPA] has less than unit dependence each [AA] [Alkali] retarding effect [IO] catalysed uncatalysed cases. [Ru(III)] unity. active species DPA understood to be as monoperiodatoargentate(III) (MPA) been shown proceed via MPA–allyl complex, which decomposes rate determining step give products. In reaction, it Ru(III)-allyl further reacts with one molecule MPA constants involved different steps mechanisms calculated for reactions. catalytic (Kc) also temperatures. activation parameters respect slow computed discussed thermodynamic quantities determined Copyright © 2007 John Wiley & Sons, Ltd.