Studies of the ruthenium(III) complexes. XII. Kinetic studies of the deammonation-anation reactions of halogenopentaammineruthenium(III) complexes in the solid state.
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概要
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The kinetics of the thermal substitution reaction of chloro- and bromopentaammineruthenium(III) complexes has been studied in the solid state. The reaction rates and kinetic parameters were determined for these reactions: [RuX(NH<SUB>3</SUB>)<SUB>5</SUB>]Y<SUB>2</SUB>(s)→[RuXY(NH<SUB>3</SUB>)<SUB>4</SUB>]Y(s)+NH<SUB>3</SUB>(g), and (X=Cl, Br: Y=Cl, Br, I, NO<SUB>3</SUB>). The values of the rate constant (s<SUP>−1</SUP>), the activation energy (kcal mol<SUP>−1</SUP>), and the activation entropy (cal mol<SUP>−1</SUP> K<SUP>−1</SUP>) were 1.70×10<SUP>−5</SUP> (at 222 °C), 41.8, and 0.7 for [RuCl(NH<SUB>3</SUB>)<SUB>5</SUB>]Cl<SUB>2</SUB>; 1.02×10<SUP>−4</SUP> (at 226 °C), 30.2, and −19.6 for [RuCl(NH<SUB>3</SUB>)<SUB>5</SUB>]Br<SUB>2</SUB>; 1.35×10<SUP>−4</SUP> (at 208 °C), 25.3, and −26.6 for [RuCl(NH<SUB>3</SUB>)<SUB>5</SUB>]I<SUB>2</SUB>; 8.47×10<SUP>−3</SUP> (at 162°C), 29.7, and −11.5 for [RuCl(NH<SUB>3</SUB>)<SUB>5</SUB>](NO<SUB>3</SUB>)<SUB>2</SUB>; 1.26×10<SUP>−4</SUP> (at 219 °C), 21.8, and −35.1 for [RuBr(NH<SUB>3</SUB>)<SUB>5</SUB>]Cl<SUB>2</SUB>, and 1.17×10<SUP>−3</SUP> (at 162 °C), 14.7, and −40.0 for [RuBr(NH<SUB>3</SUB>)<SUB>5</SUB>](NO<SUB>3</SUB>)<SUB>2</SUB> respectively. The <I>S</I><SUB>N</SUB>1-like mechanism is favorable for the deammonation-anation reaction of all the chloropentaamine series except for the iodide, while the <I>S</I><SUB>N</SUB>2-like mechanism is more probable for the corresponding reaction of the bromopentaammine series. The reaction mechanism is predominantly controlled by the coordinating ability of the inner-sphere halide ion and secondarily by that of the outer-sphere anion.
- 公益社団法人 日本化学会の論文
著者
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Kohata Susumu
Department Of Bioengineering Yatsushiro National College Of Technology
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Iwasaki Noriko
Department Of Otorhinolaryngology Kanazawa Medical University
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Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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Nishimori Masanobu
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Shimura Yoshiaki
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Iwasaki Noriko
Department of Chemistry, Faculty of Science, Kumamoto University
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