Abstract
The ^19^F NMR spectra of a series of fluorinated cyclopropanes, most of which contain chlorine or bromine on the ring, have been observed and analyzed. A scheme has been developed to assign the resonances and the molecular stereochemistry, based on substituent effects, comparison of related molecules, and isotope shifts induced by the halogens. Replacement of fluorine by chlorine shifts cis fluorine resonances to lower field, and bromine has an even greater downfield influence. However, the shift effect of bromine compared to chlorine on gem or trans fluorines is variable. The magnitude of the isotope shifts is found to be regularly related to the geometrical relationship of the halogen to the observed fluorine and thus makes a significant contribution to the fluorine assignments. The three‐bond spin–spin coupling constants between fluorine atoms in cyclopropanes display unusual behavior and are not helpful for assignment of the fluorine resonances. The signs of the coupling constants have been investigated by spin‐tickling experiments, and the previously developed relation of the coupling constant sign to its temperature dependence has been found to be violated for some molecules. Copyright © 2007 John Wiley & Sons, Ltd.