First examples of alk-1-yn-1-yliodine (V) molecules, CF3CCIF4 and C6F13CCIF4, were prepared by fluorination of the corresponding 1-iodoperfluoroalk-1-ynes with XeF2 in 1, 1, 1, 3, 3-pentafluorobutane (PFB) in the presence of BF3. The reaction of 1-iodo-2-(4- heptafluorotolyl) ethyne, 4-CF3C6F4CCI, with XeF2 (1.5 equiv) and BF3 resulted in a mixture of 4-CF3C6F4CCIF2 (main product), 4-CF3C6F4CCIF4, and trans-(4-CF3C6F4) ...