Kinetics and mechanism of the oxidation reaction of bis(.MU.-dibutyldithiocarbamato-S,S')-digold(I) by halogens.
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概要
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Kinetics of the reaction of bis(μ-dibutyldithiocarbamato-<I>S</I>,<I>S</I>′)-digold(I), [Au(<I>n</I>-Bu<SUB>2</SUB>dtc)]<SUB>2</SUB>, with I<SUB>2</SUB>, IBr, and Br<SUB>2</SUB> in dichloromethane was studied by the stopped-flow technique. A 1 : 1 charge-transfer (CT) complex, [Au(<I>n</I>-Bu<SUB>2</SUB>dtc)]<SUB>2</SUB>·X<SUB>2</SUB> (X<SUB>2</SUB>=I<SUB>2</SUB>, IBr, and Br<SUB>2</SUB>), formed in the initial process of reaction was identified spectrophotometrically at −50 °C. The rates of reaction were almost the same for I<SUB>2</SUB>, IBr, and Br<SUB>2</SUB>, and independent of the both [Au(<I>n</I>-Bu<SUB>2</SUB>dtc)]<SUB>2</SUB> and halogen concentrations. The reaction has been interpreted to proceed <I>via</I> the charge-transfer complex, [Au(<I>n</I>-Bu<SUB>2</SUB>dtc)]<SUB>2</SUB>·X<SUB>2</SUB>, which decomposes in a rate-determining step to give the final product, [Au<SUP>III</SUP>(<I>n</I>-Bu<SUB>2</SUB>dtc)<SUB>2</SUB>][Au<SUP>I</SUP>X<SUB>2</SUB>]. The activation parameters for the reactions were determined: Δ<I>H</I><SUP>\neweq</SUP>(kJ/mol)=43.7 (I<SUB>2</SUB>), 26.0 (IBr), and 12.3 (Br<SUB>2</SUB>); Δ<I>S</I><SUP>\neweq</SUP>(J/mol K))=−91.5 (I<SUB>2</SUB>), −156 (IBr), and −201 (Br<SUB>2</SUB>).
- 公益社団法人 日本化学会の論文
著者
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Itoh Kazuyuki
Department Of Biology Osaka Medical Center For Cancer And Cardiovascular Diseases
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Tanaka Koji
Department Of 1st Internal Medicine Osaka Medical College
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Kita Hidetoshi
Department of Advanced Materials Science & Engineering, Faculty of Engineering, Yamaguchi University
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Tanaka Toshio
Department of Applied Chemistry, Faculty of Engineering, Osaka Univeristy
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