| Abstract: | Interactions of nitrosonium tetrafluoroborate and hexafluorophosphate with 18-crown-6, 15-crown-5, and 12-crown-4 in dichloromethane, acetonitrile, and nitromethane have been probed by a combination of proton magnetic resonance spectroscopy, infrared spectroscopy, and conductance measurements. The stoichiometrics of the crown ether-nitrosonium salt complexes were one mole of 18-crown-6 per mole of nitrosonium salt and two moles of 12-crown-4 per mole of nitrosonium salt in all solvents. For 15-crown-5, the one-to-one stoichiometry observed in acetonitrile and nitromethane changed to two moles of crown ether per mole of nitrosonium salt in dichloromethane. The nature of these complexes is discussed. Treatment of a solution of equimolar nitrosonium hexafluorophosphate and 18-crown-6 in dichloromethane with water produced hydronium hexafluorophosphate-18-crown-6 complex. |
