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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 8, Number 6
BKCSDE 8(6)
June 20, 1987 

 
Title
Theoretical Studies of Solvent Effects on Gas Phase Reactions of Methoxide Ion with Substituted Ethylenes
Author
Ikchoon Lee*, Bon-Su Lee, Jong Ok Won
Keywords
Abstract
Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, CH2 = CHR where R = CN, CHO and NO2, 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 β-addition, in which the excess energy is forced to be contained within the β-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 α-H+ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.
Page
444 - 449
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