Studies of Ruthenium Complexes. IV. The Solvent Effect on the Isotopic Ligand-exchange Reaction of the <I>cis</I>- Dibromotetraammineruthenium(III) Complex
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概要
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The isotopic ligand-exchange reactions of <I>cis</I>-dibromotetraammineruthenium(III) were studied in aqueous and methanol-water solutions in order to distinguish them from those in the case of the monobromocomplex and in order to ascertain the role of the water molecule with respect to the reaction mechanism. In an aqueous solution, the reaction proceeds through the rate-determining aquation step with the <I>S</I><SUB>N</SUB>2 mechanism: Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUB>2</SUB><SUP>+</SUP>+H<SUB>2</SUB>O→Ru(NH<SUB>3</SUB>)<SUB>4</SUB>(H<SUB>2</SUB>O)Br<SUP>2+</SUP>+Br<SUP>−</SUP>, Ru(NH<SUB>3</SUB>)<SUB>4</SUB>(H<SUB>2</SUB>O)Br<SUP>2+</SUP>+<SUP>*</SUP>Br<SUP>−</SUP>→Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUP>*</SUP>Br<SUP>+</SUP>+H<SUB>2</SUB>O. This result is similar to that for the monobromocomplex. In the methanol solution (H<SUB>2</SUB>O∼1.5%), the exchange reaction proceeds through the <I>S</I><SUB>N</SUB>1 mechanism: Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUB>2</SUB><SUP>+</SUP>→Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUP>2+</SUP>+Br<SUP>−</SUP>, Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUP>2+</SUP>+<SUP>*</SUP>Br<SUP>−</SUP>→Ru(NH<SUB>3</SUB>)<SUB>4</SUB>Br<SUP>*</SUP>Br<SUP>+</SUP>. When the concentration of water becomes very low, the number of solvated water molecules decreases; therefore, the coordinated bromide ion may easily be liberated. When the concentration of water is higher than 10%, the rate constant increases with the increase in the water concentration. Since the electronic spectra did not change during the exchange reaction, it would seem that the water molecule attacks a <I>cis</I>-position as a nucleophile. These results can be interpreted by postulating a hydrogen-bond between the proton of the water molecule and the coordinated bromide ion.
- 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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Yamada Takato
Department of Physics, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602
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Hiroshima Yutaka
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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Hosoyamada Yoshihiro
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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