[(C6F5)2IF2][BF4], the First Salt with the Electrophilic Cation [(C6F5)2IF2]+: Synthesis,Reactivity, and Structure

The substitution of hypervalently bonded fluorine atoms in C₆F₅IF₄ was performed with C₆F₅BF₂ and resulted in the new salt [(C₆F₅)₂IF₂][BF₄]. 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 [(C₆F₅)₂IF₂]⁺ was exemplified in reactions with monovalent iodine compounds (C₆F₅I, p‐FC₆H₄I, and I₂) and with electron‐poor tri(organyl)pnictanes ER₃ (E = P, As, Sb, Bi; R = C₆F₅). In a heterogeneous reaction with CsF in MeCN the [(C₆F₅)₂IF₂]⁺ cation forms the dinuclear [{(C₆F₅)₂IF₂}₂F]⁺ cation.