Although literature abounds with examples of formation of perhaloalkanes by photo-lytic or Lewis-acid induced halogen exchange reactions involving radical or carbocationintermediates,the procedures are seldom applicable to the preparation of perhaloalkanes ingood yields under mild conditions.Recently,we have reported the spontaneous reactionsof some perhalofluoroalkanes with various types of nucleophiles.All these reactions areinitiated by the halophilic attack of nucleophiles on C—Br or C—Cl bonds,followed byanionic chain steps involving carbanion as well as olefin intermediates.Notably,the latter areformed after the β-elimination of a good leaving group from the former.On the other hand,it is well known that halogenated carbanions can effectively make halophilic attacks on theC—X bonds of other halogenated substrates,e.g.,in the“halogen dance”of Bunnett.There- Although literature abounds with examples of formation of perhaloalkanes by photo-lytic or Lewis-acid induced halogen exchange reactions involving radical or carbocationintermediates, the procedures are seldom applicable to the preparation of perhaloalkanes ingood yields under mild conditions. Recently, we have reported the spontaneous reactionsof some perhalofluoroalkanes with various types of nucleophiles. All these reactions are iniated by the halophilic attack of nucleophiles on C-Br or C-Cl bonds, followed by anionic chain steps involving carbanion as well as olefin intermediates. Notably, the latter isformed after the β-elimination of a good leaving group from the former. On the other hand, it is well known that halogenated carbanions can effectively make halophilic attacks on the C-X bonds of other halogenated substrates, eg, in the “halogen dance” of Bunnett. There-