Premium
Electron‐Density Relaxation and Oppositely Signed Reaction Constants in Dual Substituent Parameter Relationships in Dediazoniation Reactions
Author(s) -
Glaser Rainer,
Horan Christopher J.,
Zollinger Heinrich
Publication year - 1997
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199722101
Subject(s) - chemistry , substituent , relaxation (psychology) , computational chemistry , basis (linear algebra) , reaction rate constant , interpretation (philosophy) , organic reaction , dual (grammatical number) , thermodynamics , quantum mechanics , medicinal chemistry , mathematics , physics , organic chemistry , kinetics , philosophy , linguistics , psychology , social psychology , geometry , catalysis
Why are there so few exceptions to the fact that ρ R /ρ F = λ is positive? A straightforward theoretical basis is provided for the interpretation of the dediazoniation of benzenediazonium ions, one of the most prominent examples of the few reactions for which the reaction constants ρ R and ρ F [Eq. (1)] have opposite signs. The results support the model that describes CN bonding as synergistic N → C σ dative and C → N π backdative bonding. The analysis furnishes details about the electronic structure that cannot be deduced from physical–organic studies alone.