Studies of Ruthenium Complexes. III. Kinetics of Isotopic Ligand-Exchange Reactions of Halogenopentaammineruthenium(III) Complexes in Aqueous Solution
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概要
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Kinetic studies of isotopic ligand-exchange reactions, [Ru(NH<SUB>3</SUB>)<SUB>5</SUB>X]<SUP>2+</SUP>+X<SUP>*−</SUP>=[Ru(NH<SUB>3</SUB>)<SUB>5</SUB>X<SUP>*</SUP>]<SUP>2+</SUP>+X<SUP>−</SUP>, where X=Cl, Br, and I, have been made in aqueous solutions. The effects of the hydrogen- and halide-ion concentrations, and of the ionic strength of the aqueous solution on the exchange rate had not been observed under certain definite experimental conditions. The rate constants were determined to be 3.15×10<SUP>−4</SUP> sec<SUP>−1</SUP> for the chloro-pentaammine 3.63×10<SUP>−4</SUP> sec<SUP>−1</SUP> for the bromopentaammine, and 1.1×10<SUP>−4</SUP> sec<SUP>−1</SUP> for the iodopentaammine at 80°C. The energies of activation were 20 kcal/mol (chloropentaammine), 23 kcal/mol (bromopentaamine), and 30 kcal/mol (iodopentaammine). The reactions proceed through the following two steps:<BR>[Ru(NH<SUB>3</SUB>)<SUB>5</SUB>X]<SUP>2+</SUP>+H<SUB>2</SUB>O→[Ru(NH<SUB>3</SUB>)<SUB>5</SUB>H<SUB>2</SUB>O]<SUP>3+</SUP>+X<SUP>−</SUP><BR>[Ru(NH<SUB>3</SUB>)<SUB>5</SUB>H<SUB>2</SUB>O]<SUP>3+</SUP>+X<SUP>*−</SUP>→[Ru(NH<SUB>3</SUB>)<SUB>5</SUB>X<SUP>*</SUP>]<SUP>2+</SUP>+H<SUB>2</SUB>O<BR>The first step is regarded as the rate-determining one.
- 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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Takebayashi Noriyuki
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Shinohara Tetsuo
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Yamada Takato
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Hiraki Shun-ichi
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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