Bulletin of the Korean Chemical Society

  • 제8권6호
  • /
  • Pages.444-449
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  • 1987
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Theoretical Studies of Solvent Effects on Gas Phase Reactions of Methoxide Ion with Substituted Ethylenes$^\dag$

  • 발행 : 1987.12.20
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초록

Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, $CH_2$ = CHR where R = CN, CHO and $NO_2$, are investigated theoretically using the AM1 method. Results show that the methoxide approaches in-plane in all reactions, but subsequently rotate out-of-plane to form tetrahedral complexes in additon reactions. All reactions of a bare methoxide are found to be exothermic, the exothermicity being the greatest in the ${\beta}$-addition, in which the excess energy is forced to be contained within the ${\beta}$-adduct rendering extreme instability. However a part of the excess energy can be removed by a solvate molecule giving a stable complex prior to the product formation. The hydride transfer processes were found to be unfavorable due to the high activation barriers. The ${\alpha}-H^+$ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.

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참고문헌

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