Mapping Perfluoroalkyl Effects in Togni‐Type Reagents by Thermolysis

We present the thermolysis of cyclic hypervalent iodine(III) perfluoroalkyl transfer reagents carried out in standard GC‐MS instrumentation. Through heating, these structures undergo fragmentation to afford perfluoroalkyl radicals F2n+1Cn. and each reagent can be characterized by means of a threshold temperature, TIP(n). This parameter TIP(n) not only reflects the stability of the F2n+1Cn–I bond, but potentially also carries information regarding fundamental properties of the linear perfluoroalkyl chains. The heat is on: Through heating, cyclic hypervalent iodine(III) perfluoroalkyl transfer reagents undergo fragmentation to afford perfluoroalkyl radicals F2n+1Cn.. The reagents can be characterized by means of a threshold temperature, TIP(n), at which the process occurs efficiently. This parameter TIP(n) not only reflects the stability of the F2n+1Cn–I bond but may also carry information on fundamental properties of the linear perfluoroalkyl chains.