A Widely Applicable Synthetic Approach to Alk‐1‐yn‐1‐yl(polyfluoroorganyl)‐iodonium Salts [(RC≡C)(R′)I][BF4]

The reaction of alkynyldifluoroboranes RC≡CBF₂ (R = (CH₃)₃C, CF₃, (CF₃)₂CF) with organyliodine difluoride R′IF₂ bearing electron‐withdrawing polyfluoroorganyl groups R′ = C₆F₅, (CF₃)₂CFCF=CF, C₄F₉, and CF₃CH₂ leads to the corresponding alkynyl(organyl)iodonium salts [(RC≡C)(R′)I][BF₄]. This approach uses a widely applicable method as demonstrated for a representative series of polyfluorinated aryl‐, alkenyl‐, and alkyliodine difluorides. Generally, these syntheses proceed with good yields and deliver pure iodonium salts. The distinct electrophilic nature of their [(RC≡C)(R′)I]⁺ cations is deduced from multinuclear magnetic resonance data. Within the series of new iodonium salts [CF₃C≡C(C₄F₉)I][BF₄] is an intrinsic unstable one and decomposed forming CF₃C≡CI and C₄F₁₀.