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Polar Effects on Radical Addition Reactions: An Ambiphilic Radical

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Free Radicals in Synthesis and Biology

Part of the book series: NATO ASI Series ((ASIC,volume 260))

Abstract

Absolute rate constants are presented for the radical •CH2COOC(CH3)3 to 19 mono- and 1,1-disubstituted ethenes in acetonitrile. They vary with the substituents in the range 4.104 ≤ k ≤ 3106M-1s-1. Plots of logk vs ionization energies and electron affinities of the olefins yield U-shaped curves. This shows that both SOMO-LUMO and SOMO-HOMO interactions in the transition state lower the activation energy as expected from simple FMO-concepts.

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Author information

Authors and Affiliations

  1. Physikalisch-Chemisches Institut der Universität, Winterthurerstrasse 190, CH-8057, Zürich, Switzerland

    I. Beranek & H. Fischer

Authors
  1. I. Beranek
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  2. H. Fischer
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Editors and Affiliations

  1. Department of Chemistry, Politecnico di Milano, P. L. da Vinci 32, 20133, Milano, Italy

    Francesco Minisci

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© 1989 Kluwer Academic Publishers

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Beranek, I., Fischer, H. (1989). Polar Effects on Radical Addition Reactions: An Ambiphilic Radical. In: Minisci, F. (eds) Free Radicals in Synthesis and Biology. NATO ASI Series, vol 260. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0897-0_23

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  • DOI: https://doi.org/10.1007/978-94-009-0897-0_23

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6892-5

  • Online ISBN: 978-94-009-0897-0

  • eBook Packages: Springer Book Archive

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