Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetics of Isotopic Exchange between Acetylacetone-14C and Bisacetylacetonatopalladium(II) in Organic Solvents
Kazuo SaitoMichihiko Takahashi
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1969 Volume 42 Issue 12 Pages 3462-3466

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Abstract

Bisacetylacetonatopalladium(II) [Pd acac2] was precipitated crystalline free from excessive acetylacetone (Hacac) by adding the reaction mixture in anisole, benzene or 1,2-dichloroethane to chilled petroleum ether. Its specific counting rate was measured by liquid scintillation technique. The isotopic exchange rate is measurable at 40 to 80°C and the kinetics is expressed by the ordinary two term formula, Rate=[Pd acac2](k1+k2[Hacac]). The second term corresponds to the reagent path, in which acetylacetone molecule rather than acetylacetonate anion acts as nucleophilic reagent. The first term seems to express a dissociation mechanism rather than the solvent path; the break of Pd–O bond without the aid of nucleophilic attack by the solvent molecule is responsible for determining the exchange rate. The exchange reaction is accelerated by acids, and the acid-catalyzed reaction path operates independent of the reagent path to give the following kinetic formula:
Rate=[complex](k1+k2[Hacac]+k3[acid])

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