Origin of the E.S.R. hyperfine anisotropy and the cos2θ rule of the β-fluorine couplings

Abstract

The origin of the hyperfine couplings of β-fluorine nuclei in free radicals has been studied using the hyperfine tensors determined for and in single crystals. The direction of the maximum principal element of the β-fluorine coupling tensor in was found to be very close to the direction of the maximum overlap of the fluorine 2p π orbital with the half-filled carbon 2p π orbital. This means that the spin density in the fluorine 2p π orbital is mainly due to the direct overlap with the carbon 2p π orbital and the contributions from the hyperconjugation and the spin polarization mechanisms are less important. The cos²θ rule, B ₀ + B cos²θ, for the β-fluorine coupling tensor was also derived from the conformational dependence of the overlap integral. Using the ratio of B/B ₀ calculated from the overlap integral together with the observed hyperfine tensor for , the absolute values of B ₂ and B were determined and results were applied to the β-fluorine coupling tensor of the rotating CF₃ group in . The calculated tensor is in very good agreement with the one observed.