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) : Politzer, Peter ; Lane, Pat ; Grice, M. E.

PDF Url : ADA310958

Report Date : 05 JUL 1996

Pagination or Media Count : 9

Abstract : We have shown, through density functional calculations (Becke exchange/Lee, Yang and Parr correlation functionals, 6-31G** basis set) that the elimination of HF from H3C-NF2 is thermodynamically favored, Delta G(298.15 K) = -29 kcal/mole, but has a relatively high activation barrier, Delta G(double dagger)(298.15 K) = 38 kcal/mole. The N-F dissociation energy, Delta E sub(N-F), is found to be 69 kcal/mole. Introduction of a nitro group, giving H2C(NO2)NF2, produces only small changes in these values: Delta G(298.15 K) = -28 kcal/mole; Delta G(double dagger)(298.l5 K) = 36 kcal/mole; Delta E sub(N-F) = 66 kcal/mole. Replacement of all alpha hydrogens by methyl groups increases the N-F dissociation energies slightly (<2 kcal/mole). These substituent effects are interpreted in terms of geminal interactions.

Descriptors :   *HYDROGEN, *CHEMICAL BONDS, *AMINES, *FLUORINE, *ENERGETIC PROPERTIES, *ELIMINATION, *NITRO RADICALS, *HYDROGEN FLUORIDE, DENSITY, HIGH FREQUENCY, ACTIVATION, COMPUTATIONS, METHYL RADICALS, INTERACTIONS, THERMODYNAMICS, CARBON, BARRIERS, DISSOCIATION, EXCHANGE, CLEAVAGE, NITROGEN COMPOUNDS, FLUOROAMINES.

Subject Categories : Inorganic Chemistry
      Organic Chemistry
      Physical Chemistry
      Quantum Theory and Relativity
      Thermodynamics

Distribution Statement : APPROVED FOR PUBLIC RELEASE