Reactions of oxides of nitrogen with the Group V pentafluorides and stannic fluoride

Abstract

The pentafluorides of phosphorus, arsenic, and antimony have been treated with inter alia, nitric oxide, dinitrogen trioxide, nitrogen dioxide, and dinitrogen pentoxide, and stannic fluoride has been treated with nitrogen dioxide.

Nitric oxide does not combine chemically with phosphorus pentafluoride, and yields only a single involatile phase, NOAsF₆, with arsenic pentafluoride. The other reactions yield complex mixtures, all of which contain nitrosonium and/or nitronium salts. Evidence is presented for the formation of complex oxyfluoride species containing anions of general formula [MOF₄]^–(M = P, As, Sb). The [Sb₂F₁₁]^– anion is frequently formed in reactions involving antimony pentafluoride.

Antimony pentafluoride reacts with oxides of nitrogen in the liquid phase to form nitrito- or nitrato-fluorides, and stannic fluoride also forms a nitrato-fluoride when treated with liquid dinitrogen tetroxide.