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σ-Dative and π-Backdative Phenyl Cation-Dinitrogen Interactions and Opposing Sign Reaction Constants in Dual Substituent Parameter Relations
Journal of Organic Chemistry
  • Rainer Glaser, Missouri University of Science and Technology
  • Christopher J. Horan
  • Michael A. Lewis
  • Heinrich U. Zollinǵer
Abstract

For the overwhelming number of reactions studied with dual substituent parameter treatments, the ratio of the reaction constants ρR/ρF = λ is positive and close to unity. Dediazoniations are prominent representatives of the very few unusual reactions for which dual substituent parameter (DSP) relations yield reaction constants of opposing sign. To understand this exceptional behavior, we have studied with ab initio methods the energetic, structural, and electronic relaxations along the unimolecular, linear dediazoniation path of benzenediazonium ions X-1 to form phenyl cation X-2 in detail for the parent system and two important derivatives (X = H, NH2, NO2). The results support the electron density based model that describes CN bonding in X-1 by synergistic σ-dative N → C and C → N π-backdative bonding. The analysis provides a theoretical basis for the interpretation of the opposing sign DSP relationship and, in addition, furnishes details about the electronic structure that cannot be deduced from physical-organic studies alone. Polarizations in the σ-frames critically affect structures (Q values) and electronic structures (populations), and consistent explanations of structural and energetic relaxations in the course of the dediazoniation reactions require their explicit consideration. The classical tool of π-electron pushing does not suffice to provide a correct account of the electronic structures. In particular, the analysis resolves the apparent paradox that the amino group can function as an electron donor even though it is negatively charged. If σ-polarizations dominate in cases where they counteract π-effects, it would seem reasonable to assume that they also are of comparable magnitude where σ- and π-effects act in concert. In the later case, explanations based on π-polarizations might therefore seem consistent but they might lack a physical basis.

Department(s)
Chemistry
Keywords and Phrases
  • deamination,
  • DNA alkylation,
  • molecular interaction,
  • polarization
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 1999 American Chemical Society (ACS), All rights reserved.
Publication Date
1-1-1999
Publication Date
01 Jan 1999
Disciplines
Citation Information
Rainer Glaser, Christopher J. Horan, Michael A. Lewis and Heinrich U. Zollinǵer. "σ-Dative and π-Backdative Phenyl Cation-Dinitrogen Interactions and Opposing Sign Reaction Constants in Dual Substituent Parameter Relations" Journal of Organic Chemistry Vol. 64 Iss. 3 (1999) p. 902 - 913 ISSN: 0022-3263; 1520-6904
Available at: http://works.bepress.com/rainer-glaser/149/