Semiempirical quantum-chemical investigation of fragmentation of O-fluorosulfonyl-N,N-difluorohydroxylamine anion-radical

Abstract

The semiempirical quantum-chemical method PM3 has been used to calculate the heats of reaction for the decomposition of the anion-radical of O-fluorosulfonyl-N,N-difluorohydroxylamine in the gas phase and in solution. It has been shown that the reaction of the anion-radical leading to the formation of the radical.NF2 is thermodynamically favorable, either in the gas phase or in solution. For this exothermic reaction, a section of the potential energy surface along the reaction coordinate has been calculated, and it has been found that the reaction proceeds with virtually no barrier:Ea=1 kcal/mole. The O-fluorosulfonyl-N,N-difluorohydroxylamine is characterized by a high electron affinity (∼3 eV); i.e., its interaction with nucleophiles with a low ionization potential may proceed through anSRN1 mechanism.