Abstract

AbstractThe 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.

Full Text
Paper version not known

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.