Kinetics and mechanism of ligand exchange of tris(acetylacetonato)iron(III) in acetylacetone.
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概要
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Tris(acetylacetonato[2-<SUP>14</SUP><I>C</I>])iron(III) undergoes ligand exchange in acetylacetone at 4–16 °C without side reactions. The exchange rate is expressed by Rate=(<I>k</I><SUB>a</SUB>+<I>k</I><SUB>b</SUB>[H<SUB>2</SUB>O])[complex]([complex]≈0.01 M, [H<SUB>2</SUB>O]≈0.05 M), and the rate constant (10.2 °C) and activation parameters are <I>k</I><SUB>a</SUB>=(8.9±1.2)×10<SUP>−4</SUP> s<SUP>−1</SUP>, <I>ΔH</I><SUP>\neweq</SUP>=14.4±0.9 kcal mol<SUP>−1</SUP>, <I>ΔS</I><SUP>\neweq</SUP>=−22±3 cal K<SUP>−1</SUP> mol<SUP>−1</SUP> and <I>k</I><SUB>b</SUB>=(2.22±0.20)×10<SUP>−2</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, <I>ΔH</I><SUP>\neweq</SUP>=16.9±0.4 kcal mol<SUP>−1</SUP>, <I>ΔS</I><SUP>\neweq</SUP>=−6.1±1.3 cal K<SUP>−1</SUP> mol<SUP>−1</SUP> (1 cal=4.18 J, 1 M=1 mol dm<SUP>−3</SUP>). No deuterium isotope effect on the rate. The rate-determining steps seem to correspond to the formation of intermediates containing a one-ended acac<SUP>−</SUP> and an Hacac molecule (the k<SUB>a</SUB> path), and the anion and a water molecule (the k<SUB>b</SUB> path), by the <I>S</I><SUB>N</SUB>2 mechanism.
- 公益社団法人 日本化学会の論文
著者
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Saito Kazuo
Chemistry Department, Faculty of Science, Tohoku University
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Kido Hiroaki
Chemistry Department, Faculty of Science, Tohoku University
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