Accession Number:

ADA310958

Title:

Energetics of HF Elimination and N-F Bond Cleavage in Some Difluoramines and Gem-Nitro/Difluoramines.

Descriptive Note:

Technical rept.,

Corporate Author:

NEW ORLEANS UNIV LA DEPT OF CHEMISTRY

Personal Author(s):

Report Date:

1996-07-05

Pagination or Media Count:

9.0

Abstract:

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.

Subject Categories:

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical Chemistry
  • Quantum Theory and Relativity
  • Thermodynamics

Distribution Statement:

APPROVED FOR PUBLIC RELEASE