 |
Home ©NIST, 2023 Accessibility information |
Contact Us to Submit an Article
Other Databases
NIST Standard Reference Data Program
NDRL-NIST Solution Kinetics Database
NIST Computational Chemistry Comparison and Benchmark Database
The NIST Reference on Constants, Units, and Uncertainty
Administrative Links
Title: 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals
Journal: J. Phys. Chem. A
Volume: 121
Page(s): 8675 - 8687
Year: 2017
Reference type: Journal article
Squib: 2017VAN/VYA8675-8687
Reaction:
CF3CF2CF2· → (CF3)2CF·
Reaction order:
1
Rate expression:
no rate data available
Category: Theory
Data type:
Ab initio
Comments:
Reaction potential energy surface was studied using quantum chemistry. A large variety of similar 1,2-F shift reactions in perfluoroalkyl radicals with various substient groups was also studied. It was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19−29 kcal/mol. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol if the resulting radical center was stabilized by vicinal π-bonds. No rate constant values were calculated.
View full bibliographic record.