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Energy disposal in the three‐centered elimination of df from 1,1,2‐trifluoroethane‐1‐ d 1
Author(s) -
Holmes B. E.,
Setser D. W.,
Pritchard G. O.
Publication year - 1976
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550080206
Subject(s) - chemistry , isomerization , olefin fiber , elimination reaction , carbene , activation energy , mole , medicinal chemistry , hydrogen fluoride , fragment (logic) , computational chemistry , organic chemistry , catalysis , computer science , programming language
The chemical activation data for three‐ and four‐centered hydrogen fluoride elimination from CH 2 FCDF 2 have been analyzed to assign the energy released to the olefin fragment in the three‐centered process and to estimate the threshold energies for elimination channels. Based upon the cis–trans isomerization rates of CHF = CHF, 78% of the total available energy was released to the olefin fragment for the αα channel. The analysis suggests the existence of an appreciable barrier (∼10 kcal/mole) for the reverse reaction, addition of the CH 2 FCF carbene to DF. The threshold energies for αα, αβ, and βα elimination from 1,1,2‐trifluoroethane‐1‐ d 1 were assigned as 71, 68, and 68 kcal/mole, respectively. Analysis of the chemical activation data for 1,1,2,2,‐tetrafluoroethane, without distinguishing between the three‐ and four‐centered elimination channels, suggests a threshold energy of ∼75 kcal/mole.