Perfluorovinyl radical, CF₂=CF: Matrix isolation ESR and molecular orbital study

Abstract

Perfluorovinyl radical, CF2=CF, was generated in an argon matrix by photolysis of CF2=CFI, and its ESR spectrum was observed. The spectral analysis and INDO molecular orbital calculations revealed that the radical is a σ radical and has a bent structure. The majority of the spin density (70%) is in the nonbonding σ orbital of the α-carbon. The ESR spectrum is dominated by the α-fluorine hyperfine tensor (A∥ = +271 G, A⊥ = -33 G) and the trans β-fluorine hf tensor (A∥ = +96 G, |A⊥| = 13 G). The angle between the symmetry axes of the two tensors was determined as 42 ± 2°. © 1986 American Chemical Society.