Studies of the ruthenium complexes. XI. The reaction mechanism of the base hydrolysis of halogenopentaammineruthenium(III) complexes.
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概要
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The base hydrolysis of halogenopentaammineruthenium(III) complexes, [RuX(NH<SUB>3</SUB>)<SUB>5</SUB>]X, (X=Cl, Br, and I), has been studied in a solution with a 0.03–0.2 M hydroxide ion concentration in order to clarify the reaction mechanism. Some deviations from the first-order rate plots were observed early in the reaction. By the analysis of these results, it was proved that the concentration change with time for each species participating in the reaction was expressed by a linear combination of two exponential functions. The reaction can be well accounted for by a mechanism involving <I>S</I><SUB>N</SUB>2 CB and <I>S</I><SUB>N</SUB>2 processes:<BR>& [RuX(NH_3)_5]^2++OH^-\oversetk_1\undersetk_-1\rightleftarrows[RuX(NH_3)_4(NH_2)]^++H_2O<BR>& [RuX(NH_3)_4(NH_2)]^++OH^-\oversetk_2\undersetH_2O→[Ru(OH)(NH_3)_5]^2++X^-+OH^-<BR>& [RuX(NH_3)_5]^2++OH^-\oversetk_3→[Ru(OH)(NH_3)_5]^2++X^-<BR>The rate constants, <I>k</I><SUB>1</SUB>, <I>k</I><SUB>−1</SUB>, <I>k</I><SUB>2</SUB>, and <I>k</I><SUB>3</SUB>, at 15 °C were determined to be 9.29×10<SUP>−2</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, 2.65×10<SUP>−2</SUP> s<SUP>−1</SUP>, 6.78×10<SUP>−1</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, and 1.13×10<SUP>−1</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> respectively for the chloropentaammine complex.
- 公益社団法人 日本化学会の論文
著者
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Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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Sakamoto Hiroyuki
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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Sakamoto Hiroyuki
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Makino Haruo
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Hamada Keijiro
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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