The orders of relative gas-phase basicities and ammonium ion affinities of a series of polyethers obtained by application of the kinetics method and ligand exchange technique are compared to evaluate the discrepancies of results between the two techniques. The order of gas-phase basicities determined by the ligand exchange technique in a quadrupole ion trap agrees with the order established previously by Kebarle using equilibrium methods in a high-pressure mass spectrometer. The order obtained by the kinetic method in a triple quadrupole mass spectrometer varies for the ranking of one polyether (12-crown-4), and this discrepancy is attributed to a difference in the rates of the competing dissociation pathways from the triethylene glycol dimethyl ether/12-crown-4 proton-bound adduct, owing to a substantial variation in the flexibilities of these two ethers. For the order of gas-phase ammonium ion affinities, the kinetic method results agree overall with the ligand exchange results; however, the order of ammonium ion affinities for tetraethylene glycol dimethyl ether and 15-crown-5 could not be differentiated by the ligand exchange method because of the rapidity of ammonium ion transfer between the two polyethers in both directions.
Journal of the American society for mass spectrometry4, pp.718-722