Isotopic Exchange Kinetics between Dibenzoylmethane-<SUP>14</SUP>C and Its Tris-type Complex with Aluminium (III) in Tetrahydrofuran
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概要
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Isotopic exchange kinetics between [Al(dbm)<SUB>3</SUB>] and Hdbm–<SUP>14</SUP>C (dbm<SUP>−</SUP>, anion of dibenzoylmethane in enol form) has been studied in tetrahydrofuran (THF) at 30 to 55°C. During several half lives the McKay plot gives straight lines, the AB spectrum remaining unchanged. The rate is very small in the absence of catalysts, and accelerated by water and trichloroacetic acid, but not by weak acids and pyridine. The rate is expressed by<BR>R = [complex](k_2[H_2O]+k_3'[acid]+k_3[acid][H_2O]) <BR>The Arrhenius plots of <I>k</I><SUB>2</SUB>, <I>k</I><SUB>3</SUB>′, and k<SUB>3</SUB> give an equal <I>Δ</I><SUP>\neweq</SUP> value 25.6 kcal/mol. It appears one of the ligands is present as unidentate in the intermediate state, and the break of the remaining bond is the rate-determining step.
- 公益社団法人 日本化学会の論文
著者
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Saito Kazuo
Department Chemistry Faculty Of Science Tohoku University
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Matsuzawa Kazuyo
Department of Chemistry, Faculty of Science, Tohoku University
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