Kinetics of the oxidative addition of hydrogen to chloro(acrylonitrile)-bis(triphenylphosphine)rhodium(I) in benzene.
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概要
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The reaction between chloro(acrylonitrile)bis(triphenylphosphine)rhodium(I) and hydrogen was studied by the stopped-flow method under an anaerobic condition. A solution of RhCl(CH<SUB>2</SUB>=CHCN)(PPh<SUB>3</SUB>)<SUB>2</SUB> was mixed with a benzene solution containing hydrogen under the condition of [Rh]<[H<SUB>2</SUB>]<SUB>0</SUB><[CH<SUB>2</SUB>=CHCN]. A fast decrease in the absorbance was followed by a slow increase in the absorbance, until finally the absorbance returned to the initial value. It was proved that the faster reaction was the oxidative addition of hydrogen to RhCl(CH<SUB>2</SUB>=CHCN)(PPh<SUB>3</SUB>)<SUB>2</SUB>; RhCl(CH<SUB>2</SUB>=CHCN)(PPh<SUB>3</SUB>)<SUB>2</SUB>+H<SUB>2</SUB>\overset<I>k</I><SUB>34</SUB>\underset<I>k</I><SUB>43</SUB>\rightleftharpoonsRhClH<SUB>2</SUB>(CH<SUB>2</SUB>=CHCN)(PPh<SUB>3</SUB>)<SUB>2</SUB>. The slower reaction was the process in which hydrogen was consumed in the course of the hydrogenation of acrylonitrile and RhCl(CH<SUB>2</SUB>=CHCN)(PPh<SUB>3</SUB>)<SUB>2</SUB> was reproduced. The values of the rate constants were evaluated to be <I>k</I><SUB>34</SUB>≥7.8×10<SUP>3</SUP> mol<SUP>−1</SUP> dm<SUP>3</SUP> s<SUP>−1</SUP> and <I>k</I><SUB>43</SUB>≤53 s<SUP>−1</SUP>.
- 公益社団法人 日本化学会の論文
著者
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Yamagishi Akihiko
Department Of Chemistry College Of Arts And Sciences The University Of Tokyo
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FUJIMOTO Masatoshi
Department of Chemistry, Faculty of Science, Hokkaido University
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Ohtani Yoshimi
Department of Chemistry, Faculty of Science, Hokkaido University
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