Derivatographic Studies on Transition Metal Complexes. VIII. Thermal Deaquation-Anation Reaction of <I>cis</I>-[CoX(H<SUB>2</SUB>O)N<SUB>4</SUB>]Y<SUB>2</SUB> Type Complexes in Solid Phase

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概要

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• The deaquation-anation reaction of <I>cis</I>-[CoX(H<SUB>2</SUB>O)N<SUB>4</SUB>]Y<SUB>2</SUB> type complexes, where X is chloride or bromide ion, N<SUB>4</SUB> is tetraammine or bis(ethylenediamine), and Y is chloride, bromide or nitrate ion, was investigated by means of both derivatographic and isothermal methods. Some of these reactions were found to include the stereochemical changes, the structure of reaction products formed by deaquation-anation reaction being considerably affected by the counter ionic species: the chloride complexes, where Y=Cl, were deaquated with retention of <I>cis</I>-structure, whereas the bromide complexes, where Y=Br, underwent <I>cis</I>-to-<I>trans</I> stereochemical change. According to the isothermal measurement in the isomerization of <I>cis</I>-[CoCl(H<SUB>2</SUB>O)en<SUB>2</SUB>]Br<SUB>2</SUB>·H<SUB>2</SUB>O, <I>cis</I>-[CoCl(H<SUB>2</SUB>O)en<SUB>2</SUB>]-Br(NO<SUB>3</SUB>) and <I>cis</I>-[CoBr(H<SUB>2</SUB>O)en<SUB>2</SUB>]Br<SUB>2</SUB>·H<SUB>2</SUB>O, these rates were found to obey the first-order rate law and the activation energies, <I>E<SUB>a</SUB></I>, were obtained to be 38±5, 68±6 and 37±5 kcal mol<SUP>−1</SUP> and the enthalpy changes, Δ<I>H</I>, 13.5±2.0, 7.5±2.0 and 13.3±2.0 kcal mol<SUP>−1</SUP> for the respective complexes.

• 公益社団法人 日本化学会の論文

著者

• SUZUKI Masatatsu

  Department of Chemistry, Faculty of Science, Kanazawa University

• Kyuno Eishin

  Department of Chemistry Faculty of Science Kanazawa University

• Tsuchiya Ryokichi

  Department of Chemistry, Faculty of Science, Kanazawa University

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