Electron-Transfer Reactions of Multidentate Ligand Cobalt(III) Complexes. I. The Reductions of Some Chloro(triethylenetetramine)cobalt(III) Complexes by Iron(II)
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概要
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The kinetics of Fe<SUP>2+</SUP> reductions of <I>cis</I>-α-Co(trien)Cl<SUB>2</SUB><SUP>+</SUP>, <I>cis</I>-α-Co(trien)OH<SUB>2</SUB>Cl<SUP>2+</SUP> and <I>cis</I>-β<SUB>1</SUB>-Co(trien)OH<SUB>2</SUB>Cl<SUP>2+</SUP>(trien=triethylenetetramine) have been studied at 25°C, [H<SUP>+</SUP>]=0.10 M and Σ[ClO<SUB>4</SUB><SUP>−</SUP>]=1.0 M. The second-order rate constants obtained are 4.0×10<SUP>−4</SUP> M<SUP>−1</SUP> sec<SUP>−1</SUP>, 1.6×10<SUP>−4</SUP> M<SUP>−1</SUP>sec<SUP>−1</SUP>, and 9.8×10<SUP>−5</SUP> M<SUP>−1</SUP> sec<SUP>−1</SUP> for <I>cis</I>-α-Co(trien)Cl<SUP>+2</SUP>, <I>cis</I>-α-Co(trien)OH<SUB>2</SUB>Cl<SUP>2+</SUP>, and <I>cis</I>-β<SUB>1</SUB>-Co(trien)OH<SUB>2</SUB>Cl<SUP>2+</SUP> respectively. It is demonstrated, by comparing with other rate data for the Fe<SUP>2+</SUP> reductions of <I>cis</I>-CoN<SUB>4</SUB>XCl<SUP><I>n</I>+</SUP> (N=NH<SUB>3</SUB>, 0.5 en and 0.25 trien, and X=H<SUB>2</SUB>O and Cl<SUP>−</SUP>) that the rate decreases with an increase in the number of chelate rings in the Co(III) complexes. The chelate effect of the nonbridging ligand on the electron-transfer reactions of Co(III) complexes is discussed on the basis of a model which involves the ligand-field strength of the <I>trans</I>-ligand to the bridging one, the energy needed for stretching the <I>trans</I>-group away from the Co(III) center, and the effect of the solvation.
- 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
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Yamamoto Katsumi
Department Of Anesthesiology University Of Occupational And Environmental Health School Of Medicine
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YAMAMOTO Katsumi
Department of Chemistry, Ibaraki University
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Kurimura Yoshimi
College of General Education The University of Tokyo
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Ohtsuki Toshio
Department of Chemistry, Ibaraki University
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