Derivatographic Studies on Transition Metal Complexes. V. Thermal <I>cis</I>, <I>trans</I>-<I>to</I>-<I>trans</I>, <I>cis</I> Isomerization of [CoCl<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>2</SUB>en]ClO<SUB>4</SUB> in Solid Phase

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概要

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• The complex, <I>cis</I>,<I>trans</I>-[CoCl<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>2</SUB>en]ClO<SUB>4</SUB>, regardless whether its state is monohydrate or anhydride, was isomerized to <I>trans</I>,<I>cis</I>-form by heating in a solid phase. In the kinetic study on perchlorate in a closed system, it was found that the isomerization of the hydrated compound proceeded through a second order reaction with respect to the remaining fraction of the starting compound with the activation energy, <I>E</I><SUP>≠</SUP>=29.5 kcal mol<SUP>−1</SUP>, while that of the anhydrous one proceeded through a first order reaction with <I>E</I><SUP>≠</SUP>=51.4 kcal mol<SUP>−1</SUP>. On the other hand, derivatographic analyses showed that the enthalpy change in the dehydration partly including isomerization was <I>ΔH</I>=13.9 kcal mol<SUP>−1</SUP> for the monohydrated perchlorate and the activation energy was <I>E</I><SUP>≠</SUP>=39.9 kcal mol<SUP>−1</SUP>, whereas the enthalpy change of isomerization of the anhydrous perchlorate was <I>ΔH</I>=−2.1 kcal mol<SUP>−1</SUP>. From the results, it is believed that the "Aquation-anation" mechanism on the crystal surface is predominant in the isomerization for the hydrate, but it proceeds through some intramolecular reactions for the anhydride.

• 公益社団法人 日本化学会の論文

著者

• Kyuno Eishin

  Department of Chemistry Faculty of Science Kanazawa University

• Nakata Yasuo

  Department of Chemistry, Faculty of Science, Kanazawa University

• Tsuchiya Ryokichi

  Department of Chemistry, Faculty of Science, Kanazawa University

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