Mechanistic Insights into FLP‐Catalyzed Iodoperfluoroalkylations

The frustrated Lewis pair‐catalyzed iodoperfluoroalkylation of olefins, its substrate activation mode, and catalyst degradation pathways are mechanistically investigated by kinetic measurements. The transformation most likely proceeds via coordination of the phosphane to the perfluoroalkyl iodide and involves radical intermediates. Several parallel processes are found in the frustrated Lewis pair‐catalyzed iodoperfluoroalkylation of simple olefins. Substrate coordination pathways, bond activation modes, and potential intermediates call for detailed mechanistic analysis.