Energetics of HF Elimination and N-F Bond Cleavage in Some Difluoramines and Gem-Nitro/Difluoramines.
NEW ORLEANS UNIV LA DEPT OF CHEMISTRY
Pagination or Media Count:
We have shown, through density functional calculations Becke exchangeLee, Yang and Parr correlation functionals, 6-31G basis set that the elimination of HF from H3C-NF2 is thermodynamically favored, Delta G298.15 K -29 kcalmole, but has a relatively high activation barrier, Delta Gdouble dagger298.15 K 38 kcalmole. The N-F dissociation energy, Delta E subN-F, is found to be 69 kcalmole. Introduction of a nitro group, giving H2CNO2NF2, produces only small changes in these values Delta G298.15 K -28 kcalmole Delta Gdouble dagger298.l5 K 36 kcalmole Delta E subN-F 66 kcalmole. Replacement of all alpha hydrogens by methyl groups increases the N-F dissociation energies slightly 2 kcalmole. These substituent effects are interpreted in terms of geminal interactions.
- Inorganic Chemistry
- Organic Chemistry
- Physical Chemistry
- Quantum Theory and Relativity