Kinetics and Steric Course of the Substitution of Various Olefins for the Asymmetric Olefin in <I>trans</I>(<I>N</I>,olefin)-Chloro-L-prolinato-<I>trans</I>-2-buteneplatinum(II)
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概要
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Replacement of the coordinated <I>trans</I>-2-butene in <I>trans</I>(<I>N</I>,olefin)[PtCl(L-pro)(<I>S</I>,<I>S</I>-<I>trans</I>-2-butene)] (L-pro=L-prolinate anion) by various olefins in acetone has been studied at −20 to +23 °C. The rate is proportional to concentrations of the complex and the olefin nucleophile. No solvent path is observed. The second order rate constant <I>k</I><SUB>2</SUB> (10<SUP>−4</SUP> to 10<SUP>−1</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> at 8.0 °C) can be the measure of each substitution. The <I>ΔH</I><SUP>\neweq</SUP> is around 10 kcal/mol, and <I>ΔS</I><SUP>\neweq</SUP> ranges from −25 to −46 cal/mol K. Substitution of <I>cis</I>-2-butene for the asymmetrically coordinated <I>trans</I>-2-butene-<SUP>3</SUP>H gives equal <I>k</I><SUB>2</SUB>'s on the measurement of CD strength and on that of isotopic exchange. Similar substitution of <I>trans</I>-2-butene gives significantly larger <I>k</I><SUB>2</SUB> on isotopic exchange than that on CD measurement, indicating sterically selective substitution with retention of configuration. Substitution of ethylene derivatives with various groups on the carbon atoms gives different <I>k</I><SUB>2</SUB>'s depending on the kind of substituents. The steric interaction between the olefin nucleophile and the coordinated ligands seems to be a very important factor in determining the ease of substitution.
- 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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Terai Yoshiro
Chemistry Department, Faculty of Science, Tohoku University
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Kido Hiroaki
Chemistry Department, Faculty of Science, Tohoku University
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Fujita Junnosuke
Chemistry Department, Faculty of Science, Tohoku University
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