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- W2024609969 abstract "The thermal unimolecular isomerization of fluoroethylidenes to the corresponding fluoroethylenes has been studied by the MNDO method. It has been shown that fluorine substitution on the carbene carbon increases the activation energy in comparison with the ethylidene rearrangement. To understand the reason for this increase in the activation energy, the charge-transfer effects have been analyzed. Fluorine substitution at other positions does not significantly affect the activation energies. The thermodynamic parameters for the reaction have been evaluated, using vibrational and rotational spectral data calculated in this work. RRKM calculations have been performed and high-pressure Arrhenius parameters calculated. Hydrogen–deuterium kinetic isotope effects indicate that the reaction rates are altered considerably on isotopic substitution, and the change in reaction rates depends upon the position of deuterium substitution, as well as on the number of hydrogens replaced by deuterium atoms. © 1992 John Wiley & Sons, Inc." @default.
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- W2024609969 date "1992-09-30" @default.
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- W2024609969 title "Theoretical study of the thermal unimolecular rearrangement of fluoroethylidenes" @default.
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- W2024609969 doi "https://doi.org/10.1002/qua.560440305" @default.
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