Reactions of difluoroamino-radicals. Part III. Addition to olefins

Abstract

The kinetics of addition of tetrafluorohydrazine to olefins in the gas phase which yields vicinal bisdifluoroamines, can be described in terms of the mechanism: NF₂+ Of = NF₂Of*(1); NF₂Of*= NF₂+ Of (2); NF₂Of*+ Mol = NF₂Of + Mol (3); NF₂Of = NF₂+ Of (4); NF₂Of + NF₂= Of(NF₂)₂(5); where Of is an olefin, NF₂Of* is an activated radical, and Mol is an inert molecule. Values of k₁, k₂/k₃, and k₄/k₅ have been found between 41 and 155°, and the Arrhenius parameters calculated for ethylene, but-1-ene, isobutene, 2-methylbut-2-ene, 2,3-dimethylbut-2-ene, and cyclopentane. The results from a very regular pattern of chemical behaviour when taken in conjunction with earlier results for propene and the but-2-enes. The strength of an alkyl–NF₂ bond is close to 56 kcal. mole^–1.