Kinetics and mechanism of the reactions of bis(acetylacetonato)-palladium(II) with alkylamines.
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概要
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The reactions of bis(acetylacetonato)palladium(II), Pd(acac)<SUB>2</SUB>, with alkylamines (L) such as butyl-, cyclohexyl-, diethyl-, and dipropylamines in methanol to afford [Pd(acac)L<SUB>2</SUB>](acac) obey the usual two-term rate law, rate=(<I>k</I><SUB>0</SUB>+<I>k</I><SUB>1</SUB>[L])[Pd(acac)<SUB>2</SUB>]. On the other hand, the rate of reaction of Pd(acac)<SUB>2</SUB> with diethylamine in THF and benzene is expressed by rate=(<I>k</I><SUB>1</SUB>+<I>k</I><SUB>2</SUB>[L])[L][Pd(acac)<SUB>2</SUB>]. A mechanism is proposed which presumes the hydrogen-bonding interaction of Pd(acac)<SUB>2</SUB> with methanol and amine. Intermediacy of Pd(acac)(acac-<I>C</I><SUP>3</SUP>)L in these reactions was denied on the basis of the kinetic studies, and the carbon-bonded complex was concluded to be produced <I>via</I> [Pd(acac)L<SUB>2</SUB>](acac). The equilibrium constants for the reactions, Pd(acac)<SUB>2</SUB>+2Et<SUB>2</SUB>NH\rightleftarrows[Pd(acac)(Et<SUB>2</SUB>NH)<SUB>2</SUB>(acac) and Pd(acac)(acac-<I>C</I><SUP>3</SUP>)(Et<SUB>2</SUB>NH)+Et<SUB>2</SUB>NH\rightleftarrows[Pd(acac)(Et<SUB>2</SUB>NH)<SUB>2</SUB>](acac) were determined in dichloromethane and methanol.
- 公益社団法人 日本化学会の論文
著者
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Kawaguchi Shinichi
Department Of Fundamental Energy Science Graduate School Of Energy Science Kyoto University
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Matsumoto Shinichi
Department of Chemistry, Faculty of Science, Osaka City University
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