The Solvent Effect on the Electron-Transfer Reactions of Cobalt(III) Complexes. The Reduction of the <I>cis</I>-Chloro-2-aminoethanolbis(ethylenediamine)cobalt(III) Ion by Iron(II) in Aqueous Solutions of Organic Solvents
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概要
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The solvent effect on the reduction of the textitcis-chloro-2-aminoethanolbis(ethylenediamine)cobalt(III) ion by iron(II) was investigated in aqueous solutions of dimethylsulfoxide (DMSO), dimethylformamide (DMF), ethanol, and acetone. The second-order rate constants for the reduction are 4.4×10<SUP>−5</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> in the absence of an organic solvent, 1.4×10<SUP>−3</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> in 0.20 <I>M<SUB>f</SUB></I> DMSO, 7.3×10<SUP>−4</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> in 0.20 <I>M<SUB>f</SUB></I> DMF, 1.1×10<SUP>−4</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> in 0.20 <I>M<SUB>f</SUB></I> ethanol, and 1.0×10<SUP>−4</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP> in 0.20 <I>M<SUB>f</SUB></I> acetone, at 25°C and at 0.16 M HClO<SUB>4</SUB> and Σ[ClO<SUB>4</SUB><SUP>−</SUP>]=0.60 M (<I>M<SUB>f</SUB></I>= mol fraction of organic solvent). From the kinetic and spectral data, it is suggested that the increase in the rate upon the addition of an organic solvent may be mainly due to a change in the solvation sphere of the reductant by replacing the water molecules by the organic molecules.
- 公益社団法人 日本化学会の論文
著者
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Ohashi Kousaburo
Department Of Achemistry Faculty Of Science Ibaraki University
-
Suzuki Toshio
Department Of Agronomy Faculty Of Agriculture Tohoku University
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Yamamoto Katsumi
Department Of Anesthesiology University Of Occupational And Environmental Health School Of Medicine
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Kurimura Yoshimi
College of General Education The University of Tokyo
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