Dediazoniations of Arenediazonium Ions. Part 25. Influence of Substituents on the Exchange of the Diazonio Group for External Molecular Nitrogen and on the N(α),N(β)-Rearrangement in the Diazonio Group.

Article abstract of DOI:10.1002/hlca.19880710302

The N(α), N(β)-rearrangement of the two N-atoms which can be observed in solutions of <β-15N>-labelled p-substituted benzenediazonium ions follows dual substituent parameter treatments.The reaction yields a negative field and positive resonance reaction constant (ρ_F = -3.35, ρ_R = 2.47).The magnitude of these constants is, within experimental error, the same as the respective reaction constants for solvolytic dediazonation.The exchange of the diazonio group of 15N-labelled p-substituted benzenediazonium ion yields, however, field and resonance reaction constants for the forward and reverse steps in the complex mechanism of the exchange reaction.