Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The magnitude of ${\rho}x({\rho}_{nuc})$ versus the extent of bond formation in $S_N2$ Reactions

  • Published : 1994.07.20
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Abstract

The secondary deuterium kinetic isotope effects (SDKIE) involving deuterated aniline nucleophiles are reported for the reactions of benzyl bromides and chlorides and benzoyl chlorides in acetonitrile. The benzyl systems behave normally as to the trend of changes in SDKIE with the magnitude of ${\rho}X({\rho}_{nuc})$, whereas benzoyl system shows ananomaly; ${\mid}{\rho}_X{\mid}$ decreases with increase in the extent of bond making estimated by the SDKIE. This has been ascribed to the negative charge accumulation at the reaction center carbon in the transition state. The magnitude of ${\rho}_{XY}$ is found to decrease by ca. 0.03 with ten degree rise in the reaction temperature.

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