A Study of Selected Nitronium Complexes of Nitryl Chloride

Abstract

It appeared rather logical that by combining certain anhydrides with nitryl chloride in bromine trifluoride solution, the respective nitronium complexes could be directly produced, avoiding the difficult conditions encountered when using dinitrogen tetroxide in the process of Woolf and Eneleus (2), and the rather unstable nitryl fluoride used by Aynsley (6). Since these substances were capable of acting as "acids" in bromine trifluoride, the nitryl chloride would thus be a convenient source of nitronium ions. Therefore we proceeded to first form the nitronium tetrafluorobromide complex by a direct reaction between nitryl chloride and bromine trifluoride and in turn reacting this complex in bromine trifluoride solution with the respective anhydride. Both boric anhydride and phosphoric anhydride were to be used. It did not seem likely that the nitronium trifluorochlorobromide would be produced in the reaction between nitryl chloride and bromine trifluoride, due to the extremely strong fluorinating properties of bromine trifluoride. The project was also extended to include work on the direct reaction between nitryl chloride and boron trifluoride, and also aluminum trichloride . . . From the results of these reactions it was also hoped that more conclusive statements could be issued concerning the nature of nitryl chloride in the "acid" solutions, and also in the bromine trifluoride solution. [From Introduction]