The isolation,characterization,and isomerization of cis- and trans-bis(benzonitrile)dichloroplatinum(II).
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概要
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The reaction of platinum(II) chloride with neat benzonitrile gave bis(benzonitrile)dichloroplatinum(II) as a mixture of cis and trans isomers in variable proportions, depending on the temperature. The geometry of the chromatographically separated isomers was identified on the basis of the dipole-moment and IR data. The <SUP>13</SUP>C NMR spectra in CDCl<SUB>3</SUB> also enabled us to discriminate between isomers in both chemical shift and coupling to the <SUP>195</SUP>Pt of the cyanide carbon, the resonance peak of which was utilized to follow the isomerization. The rate constant (<I>k</I><SUB>c</SUB>) for the cis-to-trans isomerization was found to be (3.8±0.3)×10<SUP>－6</SUP> s<SUP>－1</SUP> in CDCl<SUB>3</SUB> at 25 °C, ten times larger than that [<I>k</I><SUB>t</SUB>=(2.9±0.2)×10<SUP>－7</SUP> s<SUP>－1</SUP>] of the reverse reaction. The equilibrium between cis and trans strongly favored trans in CDCl<SUB>3</SUB> at 25 °C, whereas in benzonitrile the cis form was the dominant species at room temperature, while the trans form was dominant at higher temperatures.
著者
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Nakamura Yukio
Faculty Of Science Osaka City University
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Kawaguchi Shinichi
Faculty of Science Osaka City University
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Miwa Toshio
Faculty of Science, Osaka City University
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Uchiyama Toshihiko
Faculty of Science, Osaka City University
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Toshiyasu Yoshio
Science Education Institute of Osaka Prefecture
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