Preparation and stereochemistry of .DELTA.-sym-((2S,2'S)-1,1'-ethylenedipyrrolidine-2,2'-dicarboxylato)cobalt(III) complexes with various bidentate ligands.
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概要
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Cobalt(III) complexes containing (2<I>S</I>,2′<I>S</I>)-1,1′-ethylenedipyrrolidine-2,2′-dicarboxylate (<I>S</I>,<I>S</I>-epro) and a bidentate ligand were prepared and characterized. The bidentate ligands were ethylenediamine, trimethylenediamine, oxalate, glycinate, (<I>R</I>)- or (<I>S</I>)-alaninate, (<I>R</I>)- or (<I>S</I>)-valinate, (<I>R</I>)- or (<I>S</I>)-prolinate, (<I>R</I>)- or (<I>S</I>)-pipecolate, sarcosinate, or <I>N</I>-ethylglycinate. The <I>S</I>,<I>S</I>-epro ligand coordinates stereoselectively to cobalt(III) ion to take only the Δ-<I>sym</I> configuration. The stereochemistry was discussed on the basis of the electronic absorption, CD, and <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectra. The rate constants of isomerization and the Gibbs' free energy difference (<I>ca.</I> 0.9 kJ mol<SUP>−1</SUP>) between the <I>R</I>(<I>N</I>) and <I>S</I>(<I>N</I>) isomers of the sarcosinato or <I>N</I>-ethylglycinato complex were investigated in relation to the interligand interaction. The thermodynamics and mechanisms of their isomerization process were little influenced by the <I>N</I>-alkyl groups.
- 公益社団法人 日本化学会の論文
著者
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Einaga Hisahiko
Institute Of Materials Science University Of Tsukuba
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Okamoto Ken-ichi
Department Of Advanced Materials Science & Engineering Faculty Of Engineering Yamaguchi Universi
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Hidaka Jinsai
Department of Chemistry Faculty of Science Osaka University
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Okabayashi Minahiro
Department of Chemistry, University of Tsukuba
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