Cis-Trans Isomerism among the Octahedral Diaquabis(N,N- or N,N'-dialkylethylenediamine)nickel(II) Complexes and Their Thermal Reaction Products.
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概要
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The thermochemical changes in coordination structure of diaquabis(<I>N</I>,<I>N</I>- or <I>N</I>,<I>N</I>′,-dialkylethylenediamine)nickel(II) complexes ([Ni(H<SUB>2</SUB>O)<SUB>2</SUB>(diamine)<SUB>2</SUB>]X<SUB>2</SUB>·<I>n</I>H<SUB>2</SUB>O) were reinvestigated by means of TG-DTA and electronic spectroscopy at room and elevated temperatures, where diamine is <I>N</I>,<I>N</I> (or <I>N</I>,<I>N</I>′-dimethylethylenediamine (<I>NN</I>- or <I>NN</I>′-dmen) or <I>N</I>,<I>N</I>-(or <I>N</I>,<I>N</I>′)-diethylethylenediamine (<I>NN</I>- or <I>NN</I>′-deen); X is Cl<SUP>−</SUP>, Br<SUP>−</SUP>, I<SUP>−</SUP>, or NO<SUB>3</SUB><SUP>−</SUP>; <I>n</I> is 0, 1, 2, or 3. The diaqua complexes prepared were all trans except for <I>cis</I>-[Ni(H<SUB>2</SUB>O)<SUB>2</SUB>(<I>NN</I>-dmen)<SUB>2</SUB>]I<SUB>2</SUB>. The trans complexes with the symmetric (<I>N</I>,<I>N</I>′-dialkylsubstituted) diamines brought about a deaquation-anation upon heating, retaining the original trans configuration, while those with the asymmetric (<I>N</I>,<I>N</I>-dialkylsubstituted) diamines transformed into the cis complexes. In the case of the <I>NN</I>-dmen complexes, <I>cis</I>-halogenoaqua species were isolated as a stable intermediate during the thermal reactions. The complex nitrates changed to <I>trans</I>-dinitrato or <I>cis</I>-mononitrato species depending upon the diamines. The effects of the <I>N</I>-substituents in the diamines and of the anions on the patterns of thermal reactions were also discussed.
- 公益社団法人 日本化学会の論文
著者
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Uehara Akira
Department Of Chemistry Faculty Of Science Kanazawa University
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SUZUKI Masatatsu
Department of Chemistry, Faculty of Science, Kanazawa University
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Ihara Yoshinori
Laboratory Of Chemistry Faculty Of Education Kanazawa University
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Satake Yasuhiro
Department of Chemistry, Faculty of Science, Kanazawa University
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