Kinetics of thermal pyridine dissociation of Ni(N-arylsalicylideneaminato)2-(pyridine)2 in solid phase.
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概要
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The kinetics of the thermal pyridine dissociation reactions of Ni[<I>N</I>-(R-C<SUB>6</SUB>H<SUB>4</SUB>)salam]<SUB>2</SUB>py<SUB>2</SUB>, where R=H(<B>1</B>), <I>p</I>-F(<B>2</B>), <I>p</I>-CH<SUB>3</SUB>O(<B>3</B>), <I>p</I>-CH<SUB>3</SUB>(<B>4</B>), <I>p</I>-Cl(<B>5</B>), and <I>p</I>-Br(<B>6</B>), in solid phase, were analyzed by the isothermal weight-loss measurements. On pyrolysis, these pyridine adducts with an octahedral coordination geometry of Ni(II) liberated pyridine to leave products with the formula Ni[<I>N</I>-(R-C<SUB>6</SUB>H<SUB>4</SUB>)salam]<SUB>2</SUB>. The product obtained from <B>2</B> was the diamagnetic monomer, those from <B>4</B>–<B>6</B> were paramagnetic polymers with μ<SUB>eff</SUB>=(3.11–3.30) μ<SUB>B</SUB>, and that from <B>3</B> was paramagnetic with an intermediary moment of μ<SUB>eff</SUB>=1.45 μ<SUB>B</SUB>. Reaction mechanisms were different depending on the nature of R: <B>2</B> followed the contracting disk equation with <I>E</I>=163 kJ/mol; <B>3</B>–<B>6</B> followed the contracting disk equation in the initial period of the reaction (the <I>E</I><SUB>a</SUB> values were 97 for <B>3</B>, 134 for <B>4</B>, 173 for <B>5</B>, and 172 kJ/mol for <B>6</B>) and then all except <B>3</B> followed Jandar's equation, in the subsequent period. These <I>E</I><SUB>a</SUB> values were considered to reflect the bond stability between the central Ni(II) ion and the axial pyridine ligands; these values increased with an increase in the electron-withdrawing property of R. The pyridine dissociation reaction may give rise to the complexes of the monomeric square-planar or to those of the associated, polymeric octahedral structure. Which result occurs does not depend only on the tendency of the central Ni(II) ion to accept, at the apical positions, the coordinate bond from the adjacent molecules.
- 公益社団法人 日本化学会の論文
著者
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Miyokawa Kikuo
Department of Chemistry, Faculty of Science, Fukuoka University
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Masuda Isao
Department of Chemistry, Faculty of Science, Fukuoka University
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Hirashima Hidenori
Department of Chemistry, Faculty of Science, Fukuoka University
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