A comparison of the relative binding energies of H+ and NO+ to aromatic and haloaromatic bases by high pressure mass spectrometry

Abstract

Proton transfer equilibria [Formula: see text] and NO+ transfer equilibria [Formula: see text] have been studied for the following bases B, benzene, toluene, o-, m-, and p-xylene. NO+ transfer equilibria for fluoro- and chlorobenzene have also been studied. Pulsed electron beam, high-pressure ion source mass spectrometry has been used to obtain the equilibrium constant K and hence the free energy changes ΔG0 and from van't Hoff plots, ΔH0 and ΔS0. Entropy changes are in general much smaller for NO+ transfer than for H+ transfer but the magnitude of the changes in the proton affinity and NO+ affinity of toluene caused by a fluorine substituent is about the same, even though the absolute value of the proton affinity is greater by a factor of 4. The position of the F substituent on toluene has a marked effect on proton affinity but no effect on NO+ affinity. The latter appears to be responsive only to the inductive effect.