Figure 3.

Synthesis of (A) 1·HCl and (B) 2·HCl by reacting their parent iodanes with HCl (g). (C) The chloride counterion proved paramount for successful iodonium synthesis, as the remaining halide series proved ineffectual for stabilizing the nascent iodonium. (D) Anion metathesis of 1·HCl with NaBArF₂₄ afforded the corresponding salt, 1·HBArF₂₄. (E) Anion metathesis of 1·HCl with NaOTf affords the unstable salt 1·HOTf, which subsequently decomposes via reductive elimination. One decomposition product was identified as 1·HBF₄, and the X-ray structure of 1·HBF₄ (thermal ellipsoids at 50% probability) is shown [atom code: green (F); red (O); pink (B); violet (I)]. Only one of the two inequivalent molecules of 1·HBF₄ is shown. Hydrogen atoms other than the O–H atom have been omitted for clarity.