[Ar(Ar′)I][N(CF3)2], effect of fluorine substituents on aryl groups of iodonium cations and of coordinating bases on the fluoride transfer from the anion to the cation

Three prototypical fluoroaryliodonium salts with the [N(CF3)2]− anion were obtained by metathesis in the corresponding tetrafluoroborate salts [Ar(Ar′)I][BF4] (Ar/Ar′ = C6H5/4-FC6H4, 3-FC6H4/4-FC6H4, C6F5/C6F5) with in situ generated Rb[N(CF3)2]. The kinetic lability of the [N(CF3)2]− anion (potential fluoride donor like [OCF3]−) in combination with the gradual change in fluoride affinity of the three [Ar(Ar′)I]+ fluoroaryliodonium cations allowed to distinguish the fluoride acceptor property of the three [Ar(Ar′)I]+ fluoroaryliodonium cations. Coordinating solvents or ligands suppressed the fluoride transfer from the [N(CF3)2]− anion to the fluoroaryliodonium cation.