One-Electron Reduction of Carbonium Ions. III. The Effect of Added Anions on the Rate of Reduction of the Tropylium Ion with Cr(II)
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概要
- 論文の詳細を見る
The one-electron reduction of tropylium fluoroborate with Cr(II) was carried out in aqueous solution containing various anions (Cl<SUP>−</SUP>, Br<SUP>−</SUP>, SO<SUB>4</SUB><SUP>2−</SUP>, HSO<SUB>4</SUB><SUP>−</SUP>, BF<SUB>4</SUB><SUP>−</SUP> and ClO<SUB>4</SUB><SUP>−</SUP>) which were added as proton acids or as sodium salts, and the reaction rate at 25°C was measured by the use of the flow method. It was found that Cl<SUP>−</SUP>, Br<SUP>−</SUP>, and SO<SUB>4</SUB><SUP>2−</SUP> exhibit the characteristic rate-accelerating effect, whereas BF<SUB>4</SUB><SUP>−</SUP> and ClO<SUB>4</SUB><SUP>−</SUP> show a slight rate-retarding effect. From the extrapolation of the anion concentration to zero, it was indicated that this reaction can proceed even in the absence of added anions. From these findings, together with the results of chemical and spectrophotometrical analyses of the Cr(III) species, it was concluded that the reduction of the tropylium ion with Cr(II) proceeds through an electron-transfer step where the anion (Cl<SUP>−</SUP>, Br<SUP>−</SUP>, or SO<SUB>4</SUB><SUP>2−</SUP>) or the water molecule acts as a weakly interacting electron-transfer bridge. This mechanism is essentially analogous to the "inner-sphere mechanism" known in the field of inorganic metal complex chemistry.
- 公益社団法人 日本化学会の論文
著者
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Komatsu Koichi
Department Of Environmental And Biological Chemistry Fukui University Of Technology
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Okamoto Kunio
Department of Fuel Chemistry Faculty of Engineering Kyoto University
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Murai Osamu
Department of Cardiology, Kawasaki Saiwai Hospital
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Tsukada Susumu
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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