Premium
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
Author(s) -
Ravenscroft Michael D.,
Zollinger Heinrich
Publication year - 1988
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19880710302
Subject(s) - chemistry , substituent , ion , reaction rate constant , nitrogen , resonance (particle physics) , group (periodic table) , medicinal chemistry , stereochemistry , computational chemistry , kinetics , atomic physics , organic chemistry , quantum mechanics , physics
The N(α), N(β)‐rearrangement of the two N‐atoms which can be observed in solutions of [β‐ 15 N]‐labelled p ‐substituted benzenediazonium ions follows dual substituent parameter treatments. The reaction yields a negative field and a positive resonance reaction constant ( p F =−3.35, p R = 2.47). The magnitude of these constants is, within experimental error, the same as the respective reaction constants for solvolytic dediazoniation. The exchange of the diazonio group of 15 N‐labelled p ‐substituted benzenediazonium ion yields, however, field and resonance reaction constants which are close to zero. This result is attributed to cancellation of the reaction constants for the forward and reverse steps in the complex mechanism of the exchange reaction.