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Russian Chemical Bulletin

, Volume 47, Issue 8, pp 1436–1441 | Cite as

Conjugation in radical cations of benzene, ethylene, and acetylene derivatives. Nonuniversality of the resonance parameters of group 14 organoelement substituents

  • A. N. Egorochkin
  • S. E. Skobeleva
  • T. G. Mushtina
Physical Chemistry

Abstract

The first vertical ionization potentialsl 1 of molecules RπX (X=Ph, H2C=CH, and HC≡C) depend on the joint influence of the inductive, resonance, and polarizability effects of substituents X, which are characterized by parameters σ1, σR+, and σα, respectively. The mechanism of conjugation in radical cations formed upon ionization of RπX is changed as compared to neutral RπX molecules, while the substituent X becomes polarized. The conjugation and polarizability effects are strenthened in the sequence Ph < H2C=CH <HC≡C as Rπ changes from Ph to H2C=CH and HC≡C. The σR+ parameters of Si-, Ge-, and Sn-containing substituents X are dependent on the type of Rπ but are connected by linear dependences in the series of benzene, ethylene, and acetylene derivatives.

Key words

ionization potential radical cations conjugation polarizability group 14 substituents non-universality of resonance parameters 

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Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • A. N. Egorochkin
    • 1
  • S. E. Skobeleva
    • 1
  • T. G. Mushtina
    • 1
  1. 1.G. A. Razuvaev Institute of Organometallic ChemistryRussian Academy of SciencesNizhnii NovgorodRussian Federation

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