The topic of ligand exchange and reaction mechanisms of fluorinated co
mpounds is reviewed, with emphasis on the main group fluorides. Mechan
isms are divided into a series of elementary steps of bond formation a
nd bond dissociation, using the coordination model of reaction mechani
sms as an organizing principle. Included in this review is an analysis
of the stereochemical behavior of pentacoordinated molecules, as well
as a discussion of the role of impurities, anionic, cationic, free ra
dical and fluorine-bridged intermediates, and fluoride-induced reactio
ns.