Thermal stability of N-heterocycle-stabilized iodanes – a systematic investigation

The thermal stability of pseudocyclic and cyclic N-heterocycle-stabilized (hydroxy)aryl- and mesityl(aryl)-λ(3)-iodanes (NHIs) through thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) is investigated. Peak decomposition temperatures (T(peak)) were observed within a wide range between 120 and 270 °C. Decomposition enthalpies (ΔH(dec)) varied from −29.81 to 141.13 kJ/mol. A direct comparison between pseudocyclic and cyclic NHIs revealed high T(peak) but also higher ΔH(dec) values for the latter ones. NHIs bearing N-heterocycles with a high N/C-ratio such as triazoles show among the lowest T(peak) and the highest ΔH(dec) values. A comparison of NHIs with known (pseudo)cyclic benziodoxolones is made and we further correlated their thermal stability with reactivity in a model oxygenation.