Guidelines for Calculating the Enthalpies of Formation of Diazonium Salts

An approach to determining the enthalpies of formation of diazonium salts has been identified, which provides three alternative ways to establish the co‐crystallizing agent in the method. Due to the virtual absence of experimental data, the method was additionally tested by an additive approach, for which cationic contributions for 15 different diazonium structures were determined. Nitrate salts with these diazonium cations exhibit enthalpies of formation ranging from −1.65 to 40.73 kcal mol −1 for calculations involving nitrogen release from the neutral structure and from 33.16 to 74.9 kcal mol −1 when considering the neutral diazo compound. The final decision on the approach can be determined by either experimental value.