Oxidation of ketones by CERIC PERCHLORATE (cas 14338-93-3) catalysed by iridium(III)

Add time:07/29/2019    Source:sciencedirect.com

In search of economical and effective catalysts it was found that IrCl3, a sluggish catalyst in alkaline media, surpasses catalytic efficiency of osmium and ruthenium in aqueous perchloric acid medium in the oxidation of aliphatic ketones by CERIC PERCHLORATE (cas 14338-93-3). Rate decreases in the beginning at low acid concentrations, reaches to a minimum and then becomes proportional to [HClO4], probably due to conversion of hydrolysed to unhydrolysed species of ceric perchlorate, which then accelerates the rate. Reduction of oxidant by water depends on the concentrations of acid and [cerium(IV)] initially used. Orders are one with catalyst, one initially with respect to oxidant and ketones tending to become zeroth order at higher concentrations. No effect of change of μ on the rate was observed. Thermodynamic data suggest that diethyl ketone (DET) forms the activated complex more easily compared to dimethyl ketone (DMT).

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