Cobalt-59 Nuclear Magnetic Resonance Study of Cobalt(III) Complexes. Empirical Rules for the Cobalt-59 Chemical Shifts and Line Widths of [Co<SUP>III</SUP>(en)<I><SUB>x</SUB></I>(NH<SUB>3</SUB>)<SUB>6−2<I>x</I>−<I>y</I></SUB>L<I><SUB>y</SUB></I>]-type Com
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概要
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The cobalt-59 chemical shifts and line widths for about seventy cobalt(III) complexes of the [Co<SUP>III</SUP>(en)<I><SUB>x</SUB></I>(NH<SUB>3</SUB>)<SUB>6−2<I>x</I>−<I>y</I></SUB>L<I><SUB>y</SUB></I>] (L= Cl, Br, NO<SUB>2</SUB>, N<SUB>3</SUB>, OH, H<SUB>2</SUB>O, CO<SUB>3</SUB>, and C<SUB>2</SUB>O<SUB>4</SUB>) type have been measured. The cobalt-59 chemical shifts of this type of complex are approximately represented by a simple relation:<BR>δ(ppm)=360x+\oversety\underseti=1∑δ_i(L) (x=0, 1, and 2), <BR>where δ<I><SUB>i</SUB></I>(L) is the <I>i</I>-th ligand shift parameter which represents the contribution of the <I>i</I>-th ligand, L, to the total chemical shift. Three empirical rules can be derived from experimental observations: I. The chemical shift of a <I>trans</I>-isomer is higher than that of the corresponding <I>cis</I>-isomer. II. The line width of the <I>trans</I>-CoA<SUB>4</SUB>B<SUB>2</SUB> isomer is larger than that of the <I>cis</I>-CoA<SUB>4</SUB>B<SUB>2</SUB> isomer. III. The line width of a <I>meridional</I> isomer is larger than that of the corresponding <I>facial</I> isomer. Illustrative examples are presented where cobalt-59 NMR is used to identify cobalt (III) complexes and to study the kinetics and equilibrium in solution.
- 公益社団法人 日本化学会の論文
著者
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Koike Yasuo
Department Of Medical Technology Nagoya University School Of Health Science
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Yamasaki Akira
Department Of Chemistry Faculty Of Science The University Of Tokyo
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Fujiwara Shizuo
Department Of Chemistry Faculty Of Science Chiba University
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Yajima Fumikazu
Department of Inorganic Chemistry, Mitsubishi Kasei Corporation Research Center
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Yamasaki Akira
Department of Applied Chemistry and Physics, The University of Electro-Communications
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Yamasaki Akira
Department of Chemistry, Faculty of Science, The University of Tokyo
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