Electrochemical kinetic parameters of geometric isomers of singly charged cobalt(III) complexes.
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概要
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The kinetic parameters of electrode reactions of several geometric isomers of singly charged cobalt(III) complexes have been determined by means of Tast polarography. The complexes studied are <I>trans</I>-[Co(NCS)(NO<SUB>2</SUB>)(en)<SUB>2</SUB>]Cl·H<SUB>2</SUB>O, <I>cis</I>-[Co(NCS)(NO<SUB>2</SUB>)(en)<SUB>2</SUB>]Cl·2H<SUB>2</SUB>O, <I>trans</I>-[Co(NO<SUB>2</SUB>)<SUB>2</SUB>(en)<SUB>2</SUB>]NO<SUB>3</SUB>, <I>cis</I>-[Co(NO<SUB>2</SUB>)<SUB>2</SUB>(en)<SUB>2</SUB>]NO<SUB>3</SUB>, <I>trans</I>-[Co(NO<SUB>2</SUB>)<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>]NO<SUB>3</SUB>·0.5H<SUB>2</SUB>O, <I>cis</I>-[Co(NO<SUB>2</SUB>)<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>]NO<SUB>3</SUB>, <I>trans</I>-[CoCl(NO<SUB>2</SUB>)(en)<SUB>2</SUB>]NO<SUB>3</SUB>, and <I>cis</I>-[CoCl(NO<SUB>2</SUB>)(en)<SUB>2</SUB>]NO<SUB>3</SUB>. These complexes showed two irreversible reduction waves; the first corresponds to Co<SUP>III</SUP>→Co<SUP>II</SUP>, and the second, to Co<SUP>II</SUP>→Co<SUP>0</SUP>. The electrochemical kinetic parameters for the one-electron reduction wave were obtained in 0.1 and 1.0 M acetate buffer solutions. The half-wave potentials for the first wave of the complexes were more positive for the <I>cis</I> isomers than for the corresponding <I>trans</I> isomers. The cathodic rate constants at <I>E</I>=0 for the <I>cis</I> isomers were also larger than those for the corresponding <I>trans</I> isomers. A slight increase in the rate constant with the decrease in ionic strength was observed.
- 公益社団法人 日本化学会の論文
著者
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Yamada Akifumi
Department Of Chemistry Faculty Of Engineering Nagaoka University Of Technology
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Yoshikuni Tadatsugu
Research Laboratory of Otsuka Chemical Co., Ltd.
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