Thermochemical studies of substituted phenylnitrenes: Enthalpies of formation of chlorophenylnitrenes

•The 1st and 2nd N–H bond dissociation energies in anilines have been measured.•The effects of chlorination on bond dissociation energies have been investigated.•The enthalpies of formation of chlorinated phenylnitrenes have been determined.•The enthalpies of formation of triplet and singlet states of nitrenes have been determined.

The gas-phase acidities of chloroanilino-radicals have been measured, and have been combined with the electron affinities of chlorophenylnitrenes to determine the N–H bond dissociation energy of chloroanilino-radicals and the enthalpies of formation for the triplet, singlet, and radical anion states of the isomeric nitrenes. There is little difference found between the bond dissociation energies in the radicals and those in the corresponding anilines, indicating little interaction between the unpaired electrons in the chlorophenylnitrene, as expected. The values obtained are in good agreement with the values obtained from the theoretical calculations.Figure optionsDownload full-size imageDownload as PowerPoint slide