Abstract
Abstract A chiral germyl radical produced from an optically active hydrogermane, 1-NpPhMeGe*H, abstracted a chlorine atom from CCl4 to give the corresponding chlorogermane with retention of configuration. Progressive dilution of CCl4 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 (kCl⁄kinv) of the chiral germyl radical was found to be (0.52±0.13) mol−1 dm3 at 80 °C. The rate constant for the chlorine abstraction (kCl) by germyl radicals with CCl4 was determined to be (6.6±1.0)×108 s−1 mol−1 dm3 by laser-photolysis experiments. By using this rate constant, the kinv value for the chiral germyl radical was estimated to be ca. 2×109 s−1.
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