Addition of the elements of 'IF' and of 'BrF' to alkenes can be effected by the in situ generation of these electrophiles from the halogen-AgF. For cyclohexene, 3,3,6,6-tetradeuterocyclohexene, methylenecyclohexane, styrene, and indene, these reactions are simple. However, for acenaphthylene, halogen–fluorine exchange and other reactions make the overall reaction quite complex. Electrophilic addition reactions for 1-fluoro-acenaphthylene are also described. The n.m.r. spectra of many of the products are given and discussed in some detail.