[(C 6 F 5 ) 2 IF 2 ][BF 4 ], the First Salt with the Electrophilic Cation [(C 6 F 5 ) 2 IF 2 ] + : Synthesis, Reactivity, and Structure

The substitution of hypervalently bonded fluorine atoms in C 6 F 5 IF 4 was performed with C 6 F 5 BF 2 and resulted in the new salt [(C 6 F 5 ) 2 IF 2 ][BF 4 ]. The iodonium(V) salt was characterized by multi‐NMR and Raman spectroscopy and X‐ray crystal structure analysis. The fluorinating ability of the new electrophilic cation [(C 6 F 5 ) 2 IF 2 ] + was exemplified in reactions with monovalent iodine compounds (C 6 F 5 I, p ‐FC 6 H 4 I, and I 2 ) and with electron‐poor tri(organyl)pnictanes ER 3 (E = P, As, Sb, Bi; R = C 6 F 5 ). In a heterogeneous reaction with CsF in MeCN the [(C 6 F 5 ) 2 IF 2 ] + cation forms the dinuclear [{(C 6 F 5 ) 2 IF 2 } 2 F] + cation.