The reduction of cobalt(III) complexes by ascorbic acid. II. The kinetics and mechanisms of the reactions of diaqua and aquahydroxo macrocyclic N4 complexes.
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概要
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The kinetics of the reductions of several macrocyclic N<SUB>4</SUB> cobalt(III) complexes by L-ascorbic acid (H<SUB>2</SUB>A, have been studied at 25.0 °C, at an ionic strength of 0.10 mol dm<SUP>−3</SUP> (LiClO<SUB>4</SUB>), and over the pH range from 1.64 to 3.47. The second-order rate constants in dm<SUP>3</SUP> mol<SUP>−1</SUP> s<SUP>−1</SUP> are 3.4±0.6 (Me<SUB>6</SUB>[14]4,11-dieneN<SUB>4</SUB>), (4.2±0.2)×10 (Me<SUB>4</SUB>[14]tetraeneN<SUB>4</SUB>), and (4.2±0.1)×10 (<I>ms</I>-Me<SUB>6</SUB>[14]aneN<SUB>4</SUB>) for the reactions of [Co(N<SUB>4</SUB>)(H<SUB>2</SUB>O)<SUB>2</SUB>]<SUP>3+</SUP> with HA<SUP>−</SUP> ions and (1.1±0.1)×10<SUP>2</SUP> (Me<SUB>6</SUB>[14]4,11-dieneN<SUB>4</SUB>), (1.3±0.1)×10<SUP>3</SUP> (Me<SUB>4</SUB>[14]tetraeneN<SUB>4</SUB>), (5.5±0.1)×10 (<I>ms</I>-Me<SUB>6</SUB>[14]aneN<SUB>4</SUB>), and (2.9±0.6)×10 ([14]aneN<SUB>4</SUB>) for the reactions of [Co(OH)(N<SUB>4</SUB>)(H<SUB>2</SUB>O)]<SUP>2+</SUP> with HA<SUP>−</SUP> ions. The mechanisms of these reactions are discussed, and it is concluded that the lack of saturation of macrocyclic ligands facilitates the electron-transfer reaction between cobalt(III) and ascorbic acid.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Yasuo
Department Of Chemistry College Of Science Rikkyo University
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Tsukahara Keiichi
Department Of Chemistry Faculty Of Science Nara Women's University
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Izumitani Tatsuo
Department of Chemistry, Faculty of Science, Kyushu University 33
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Tsukahara Keiichi
Department of Chemistry, Faculty of Science, Shimane University
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