The interaction of organomercury compounds of the type RHgX (where X=R or Br; R=Ar or Alk) with NO 2BF 4 has been studied in sulfolane. It is shown that the reaction is a redox process leading when R=Ar to ArH as the principal product together with some ArNO 2. The main reaction path is governed by the escape of the Ar radical formed by a single-electron oxidation process from the reaction cage and its interaction with the solvent. In contrast, ArNO 2 is the main product of the reaction with nitric acid in Ac 2O. An attempt has been made to explain this difference in behaviour. Some RBr is formed when X=Br, indicating that the subsequent route of the oxidation process is very dependent on the decomposition path of the cation radical (RHgX) +. When R=Alk a nitroalkane is one of main reaction products whereas escape of the radical from the reaction cage leads not only to a hydrocarbon but also, through reaction of the radical with oxygen, to the formation of an aldehyde.