Kinetic studies of the electron transfer reactions in iron(II) and iron(III) systems. XII. The ratios of the reaction rates of the outer-sphere vs. inner-sphere electron transfer mechanisms in the presence of X- (X-=Cl-,SCN-, and N3-) in aqueous solutions
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概要
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The electron transfer reactions between Fe<SUP>2+</SUP> and FeX<SUP>2+</SUP> (X<SUP>−</SUP>=Cl<SUP>−</SUP>, SCN<SUP>−</SUP>, or N<SUB>3</SUB><SUP>−</SUP>) may take place through the inner- or outer-sphere mechanism or through both in parallel. The process of the outer-sphere mechanism is just equivalent to the process of dissociation of FeX<SUP>2+</SUP> catalyzed by Fe<SUP>2+</SUP> in appearance. When the overall rate constant of the electron transfer reaction and the rate constant of Fe<SUP>2+</SUP>-assisted dissociation reaction of FeX<SUP>2+</SUP> are denoted by <I>k</I><SUB>E</SUB> and <I>k</I><SUB>o</SUB> respectively, the fraction <I>r</I> of the outer-sphere mechanism to the total is given in terms of <I>r</I>=2<I>k</I><SUB>o</SUB>⁄<I>k</I><SUB>E</SUB>. Thus, the <I>r</I> values were determined with the results that <I>r</I>(Cl<SUP>−</SUP>)=44% at <I>I</I>=1.5 M (1 M=1 mol dm<SUP>−3</SUP>) and 25 °C, <I>r</I>(SCN<SUP>−</SUP>)=100% at <I>I</I>=0.5 M and 25 °C, and <I>r</I>(N<SUB>3</SUB><SUP>−</SUP>)=0% at <I>I</I>=0.55 M and 10 °C. These facts suggest that <I>r</I> depends considerably upon the bridging ability of X<SUP>−</SUP>; formation of binuclear intermediate may be favored by the symmetrical structure and the size of X<SUP>−</SUP>, which make the inner-sphere mechanism easier with the stronger coordinate bond and the weaker electric repulsion between the two reactants beyond the bridging ligand.
- 公益社団法人 日本化学会の論文
著者
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Wada Goro
Department of Chemistry, Faculty of Science, Nara Women s University
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Ichimura Sachiko
Department of Chemistry, Faculty of Science, Nara Women's University
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Inatani Tomiko
Department of Chemistry, Faculty of Science, Nara Women's University
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