Kinetic studies of the hydrolysis of diketene catalyzed by the chloropalladium(II) complex.
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概要
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When diketene and sodium tetrachloropalladate(II) are mixed in aqueous solution, color of the solution changes promptly from dark red to yellow. During this fast primary reaction about one equivalent of diketene is consumed and acetoacetic acid (H<SUB>2</SUB>A) is retained as a trihapto ligand in [PdCl<SUB>2</SUB>(HA)]<SUP>−</SUP> (<B>2</B>). The succeeding steady hydrolysis of diketene (S) proceeds as a pseudo first-order reaction, obeying the rate law: –d[S]/d<I>t</I>=<I>k</I><SUB>obsd</SUB>[S]=(<I>k</I><SUB>0</SUB>+<I>k</I><SUB>cat</SUB>)[S], <I>k</I><SUB>cat</SUB>=<I>k</I><SUB>obsd</SUB>–<I>k</I><SUB>0</SUB>=(<I>k</I><SUB>1</SUB>+<I>k</I><SUB>2</SUB>/[H<SUP>+</SUP>])[Pd<SUP>II</SUP>]/[Cl<SUP>−</SUP>], where <I>k</I><SUB>1</SUB>=2.0×10<SUP>−5</SUP> s<SUP>−1</SUP> and <I>k</I><SUB>2</SUB>=2.96×10<SUP>−6</SUP> mol dm<SUP>−3</SUP> s<SUP>−1</SUP> at 0 °C and μ=1.0 mol dm<SUP>−3</SUP> (HClO<SUB>4</SUB> and NaClO<SUB>4</SUB>). A mechanism which postulates complex <B>2</B> as the effective catalyst is proposed to explain the observed two-term rate equation.
- 公益社団法人 日本化学会の論文
著者
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Okeya Seichi
Faculty Of Education Wakayama University
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Kawaguchi Shinichi
Faculty of Science Osaka City University
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