Positive Ion Chemistry of Elemental Fluorine

Abstract

F2•+ ions have been generated in the external ion source of a FT-ICR mass spectrometer, and their reactivity with a choice of neutrals, ranging from noble gases to polyatomic molecules, has been investigated. With the exception of He and Ne, all neutrals react with F2•+ at the collision controlled limit, yielding predominantly electron transfer and fragmentation products. Noteworthy, a formal F+ transfer process takes place from the reaction of F2•+ with Ar, among the noble gases, and with CO and N2, among diatomic molecules. The unimolecular and bimolecular reactivity of F2H+, obtained from the F2•+ reaction with H2, allowed the proton affinity of elemental fluorine (PA = 79 ± 5 kcal mol-1) to be experimentally derived.