Bulletin of the Korean Chemical Society

  • 제9권3호
  • /
  • Pages.179-182
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  • 1988
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Correlation Between Cross Interaction Constant and Bond Length in the S$_N$2 Transition State

  • 발행 : 1988.06.20
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초록

A simple correlation between cross interaction constants ${\rho}_{ij}$ and bond lengths in the transition state was obtained ; it has been shown that ${\rho}_{ij}$ corresponds to force constant of activation, which in turn is related to bond length by Badger's rule involving only universal constants. A satisfactory correlation between 4-31G ab initio calculated values of bond length and force constant for C-X streching in the transition state of the methyl transfer reaction, $X^-\;+\;CH_3X\;=\;XCH_3\;+\;X^-$, indicated that Badger's rule can be extended to bonds in the transition state. Independence of ${\rho}_{ij}$ values from the variable charge transmission of reaction centers has been demonstrated with nearly constant, experimentally determined I${\rho}$XYI values, and hence similar degree of bond formation, for various $S_N2$ reactions.

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참고문헌

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피인용 문헌

  1. Cross-interaction constants as a measure of the transition state structure. Part 8. Mechanism of the reaction of 2-phenylethyl benzenesulphonates with benzylamine in acetonitrile vol.3, pp.8, 1988, https://doi.org/10.1002/poc.610030808
  2. Cross interaction constants as a measure of the transition state structure. 13. Steric effects of theN,N-dimethyl group on the transition state structure in aminolysis of alkyl benzenesulphonates vol.3, pp.11, 1988, https://doi.org/10.1002/poc.610031109
  3. Cross-interaction constants as a measure of the transition state structure. Part 15. Kinetic isotope effects in the SN2 reactions of 2-phenylethyl derivatives with deuterated aniline nucleophiles vol.4, pp.2, 1991, https://doi.org/10.1002/poc.610040206
  4. Theoretical studies on the gas-phase nucleophilic substitution reactions of benzyl chlorides with phenoxides and thiophenoxides vol.11, pp.2, 1988, https://doi.org/10.1002/(sici)1099-1395(199802)11:2<115::aid-poc985>3.0.co;2-b