The consequences of cation-radical fluorination theory—II : Fluorination pathways with less-reactive reagents

Abstract

The fluorination of benzene with caesium tetrafluorothallate and of pyridine or benzo[b] furan with caesium tetrafluorocobaltate gives sequences of polyfluoroaromatics with vicinal fluorines. Polynuclear aromatics are fluorinated by caesium or potassium tetrafluorocobaltate to give products containing little or no hydrogen, whereas the stronger fluorinating agent cobalt trifluoride gives products which contain much hydrogen. These two previously unexplained features are rationalized by a mechanism which involves 1,2-migrations of fluorine in cyclohexadienyl-type radicals or cations, and is backed up by CNDO/2 calculations. This rationalization implies significantly different rates of atom or ion migrations through the lattices of the different solid fluorinating agents.