Stereochemistry of a chiral germyl radical in the reaction of carbon tetrachloride.
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概要
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A chiral germyl radical produced from an optically active hydrogermane, 1-NpPhMeGe<SUP>*</SUP>H, abstracted a chlorine atom from CCl<SUB>4</SUB> to give the corresponding chlorogermane with retention of configuration. Progressive dilution of CCl<SUB>4</SUB> with cyclohexane demonstrated that the chiral germyl radical could also undergo inversion. A mechanism in which inversion of the chiral germyl radical competed with chlorine abstraction was proposed and the relative rate of chlorine abstraction to inversion (<I>k</I><SUB>Cl</SUB>⁄<I>k</I><SUB>inv</SUB>) of the chiral germyl radical was found to be (0.52±0.13) mol<SUP>−1</SUP> dm<SUP>3</SUP> at 80 °C. The rate constant for the chlorine abstraction (k<SUB>Cl</SUB>) by germyl radicals with CCl<SUB>4</SUB> was determined to be (6.6±1.0)×10<SUP>8</SUP> s<SUP>−1</SUP> mol<SUP>−1</SUP> dm<SUP>3</SUP> by laser-photolysis experiments. By using this rate constant, the <I>k</I><SUB>inv</SUB> value for the chiral germyl radical was estimated to be ca. 2×10<SUP>9</SUP> s<SUP>−1</SUP>.
- 公益社団法人 日本化学会の論文
著者
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SAKURAI Hideki
Department of Chemistry, Faculty of Science, Tohoku University
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Mochida Kunio
Department Of Chemistry Faculty Of Science Gakushuin University
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Sakurai Hideki
Department Of Chemistiy Faculty Of Science Tohoku University
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Yamauchi Takato
Department of Chemistry, Faculty of Science, Gakushuin University
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