The base-catalyzed isomerization of the bis(ethylenediamine-N-acetato)cobalt(III) complex.

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概要

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• The isomerization reaction among six geometrical isomers of [Co(edma)<SUB>2</SUB>]<SUP>+</SUP>, which were all resolved into optically active isomers except for the achiral C<I><SUB>i</SUB></I>-trans(O) isomer, has been studied in a basic aqueous solution. It has been found that the reaction is stereoselective and that the main reaction schemes may be described as follows: (1) ΛΔΛ(S,S)-C<SUB>2</SUB>-trans(O) \rightleftharpoons ΔΛΔ (R<SUP>*</SUP>,S)-C<SUB>1</SUB>-cis(O)\rightleftharpoons ΔΛ(R,R)-cis(O)trans(NH) \rightleftharpoons meso(R,S)-C<I><SUB>i</SUB></I>-trans(O)→ΛΔΛ(R,R)[or ΔΛΔ(S,S)]-cis(O)trans(NH<SUB>2</SUB>) and (2) meso(R,S)-C<I><SUB>i</SUB></I>-trans(O)←(+)<SUB>504</SUB><SUP>CD</SUP>-mer→ΛΔΛ(S,S)-C<SUB>2</SUB>-trans(O). In each of the isomerization steps of (1), the inversion occurs at one of two secondary-N centers of the coordinated edma ligands. The rate of deuteration at the secondary-NH was also measured for all geometrical isomers; a linear relationship between the rates of the deuteration and isomerization was found. It was suggested that the isomerization of the [Co(edma)<SUB>2</SUB>]<SUP>+</SUP> system proceeded through the deprotonated five-coordinated intermediates formed by Co–O bond-rupture in the conjugate-base forms.

• 公益社団法人 日本化学会の論文

著者

• Yasui Takaji

  Department Of Chemistry Faculty Of Science Kochi University

• Ama Tomoharu

  Department Of Chemistry Faculty Of Science Kochi University

• Kawaguchi Hiroshi

  Department Of Applied Chemistry Faculty Of Engineering Utsunomiya University

• Niiyama Ryuichi

  Department of Chemistry, Faculty of Science, Kochi University

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