Stereoselective substitution of trans-2-butene for the S,S-2-butene in trichloro-S,S-2-buteneplatinate(II) in acetone.
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概要
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A new complex salt [Ph<SUB>4</SUB>P][PtCl<SUB>3</SUB>(<I>S</I>,<I>S</I>-tbn[1,3-<SUP>3</SUP><I>H</I>])] (tbn, <I>trans</I>-2-butene) undergoes racemization and ligand isotopic exchange in acetone containing a large excess of tbn without side reactions. Both rates are expressed by the second order rate equations, <I>R</I><SUB>(CD)</SUB>=<I>K</I><SUB>2(CD)</SUB>[Pt][tbn] and <I>R</I><SUB>(IE)</SUB>=<I>K</I><SUB>2(IE)</SUB>[Pt][tbn], the <I>k</I><SUB>2</SUB> values being 17.6 and 70.6×10<SUP>−3</SUP>M<SUP>−1</SUP>s<SUP>−1</SUP> at 8.0 °C, respectively (M=mol dm<SUP>−3</SUP>). Individual <I>k</I><SUB>2</SUB> values for the substitutions without and with inversion of configuration of coordinated tbn are calculated to be 62.0 and 8.7×10<SUP>−3</SUP>M<SUP>−1</SUP>s<SUP>−1</SUP>, respectively, the corresponding <I>ΔH</I><SUP>\neweq</SUP> and <I>ΔS</I><SUP>\neweq</SUP> values being 36.3±3.1 and 37.6±2.7 kJ mol<SUP>−1</SUP>, and −138±12 and −149±10 J· mol<SUP>−1</SUP> Kr<SUP>−1</SUP>. Source of the stereoselectivity appears to consist in the difference in ease of formation of square pyramidal transition state on the nucleophilic attack of tbn upon the complex.
- 公益社団法人 日本化学会の論文
著者
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Saito Kazuo
Department Chemistry Faculty Of Science Tohoku University
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Terai Yoshiro
Department of Chemistry, Faculty of Science, Tohoku University
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