Preparation and solid-phase thermal cis-trans isomerization of the mixed bis(diamine)chromium(III) complexes of the type [CrX2(aa)(bb)]X nH2O.

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概要

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• The mixed bis(diamine)chromium(III) complexes <I>trans</I>- and <I>cis</I>-[CrX<SUB>2</SUB>(aa)(bb)]X·<I>n</I>H<SUB>2</SUB>O were prepared and characterized where X is chloride or bromide ion; aa and bb are different diamines selected from ethylenediamine (en), propylenediamine (pn) and trimethylenediamine (tn); and <I>n</I> is a number of 0 to 2. The <I>cis</I>-<I>trans</I> isomerization of the above complexes was investigated non-isothermally (derivatographically) and isothermally in the solid-phase. The isomerization was found to be one-way (<I>trans</I>-to-<I>cis</I>) and exothermic. The activation energies were estimated for dehydration or dehydration plus dehydrohalogenation (<I>E</I><SUB>d</SUB>) and isomerization (<I>E</I><SUB>i</SUB>. The intermediates <I>mer</I>-[CrBr<SUB>3</SUB>(en)(pn)]·2H<SUB>2</SUB>O and <I>mer</I>-[CrBr<SUB>3</SUB>(pn)(tn)]·2H<SUB>2</SUB>O were isolated during the isomerization of <I>trans</I>-[CrBr<SUB>2</SUB>(en)(pn)]Br·2H<SUB>2</SUB>O and <I>trans</I>-[CrBr<SUB>2</SUB>(pn)(tn)](H<SUB>5</SUB>O<SUB>2</SUB>)Br<SUB>2</SUB>, respectively. Bond rupture was proposed to be operative in the pathway of the isomerization.

• 公益社団法人 日本化学会の論文

著者

• Uehara Akira

  Department Of Chemistry Faculty Of Science Kanazawa University

• Mitra Samiran

  Department Of Chemistry Inorganic Chemistry Section Jadavpur University

• Tsuchiya Ryokichi

  Department of Chemistry, Faculty of Science, Kanazawa University

• Yoshikuni Tadatsugu

  Department of Chemistry, Faculty of Science, Kanazawa University

• Mitra Samiran

  Department of Chemistry, Faculty of Science, Kanazawa University

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