Electron-Density Relaxation and Oppositely Signed Reaction Constants in Dual Substituent Parameter Relationships in Dediazoniation Reactions

Abstract

Why are there so few exceptions to the fact that ρR/ρF = 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 ρR and ρF [Eq. (1)] have opposite signs. The results support the model that describes C-N 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.

Meeting Name

30th Midwest Theoretical Chemistry Conference (1997: May 22-24, Urbana-Champaign, IL)

Department(s)

Chemistry

Keywords and Phrases

Bond theory; Dediazoniation; Diazonium ions; Electronic structure; Linear free energy relation

International Standard Serial Number (ISSN)

0570-0833

Document Type

Article - Conference proceedings

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 1997 Wiley-VCH Verlag, All rights reserved.

Publication Date

01 Nov 1997

Link to Full Text

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