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Related Experiment Videos

4'-substituted-4-biphenylyloxenium ions: reactivity and selectivity in aqueous solution.

Michael Novak1, Matthew J Poturalski, Whitney L Johnson

  • 1Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA. novakm@muohio.edu

The Journal of Organic Chemistry
|May 6, 2006
PubMed
Summary

Azide trapping studies reveal biphenylyloxenium ions are generated during hydrolysis. Short-lived ions require preassociation mechanisms for trapping, differing from longer-lived ions.

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Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Computational Chemistry

Background:

  • Understanding the reactivity of transient carbocations is crucial in organic chemistry.
  • Biphenylyloxenium ions are key intermediates in various hydrolysis reactions.
  • Previous studies have explored substituent effects on carbocation stability and reactivity.

Purpose of the Study:

  • To investigate the generation and trapping mechanisms of 4'-substituted-4-biphenylyloxenium ions.
  • To differentiate between diffusional and preassociation mechanisms in ion trapping.
  • To compare the reactivity of oxenium ions with related nitrenium ions.

Main Methods:

  • Azide trapping experiments to detect transient ions.
  • Kinetic analysis of hydrolysis reactions (first-order and second-order).

Related Experiment Videos

  • 18O labeling to study bond cleavage pathways.
  • Computational chemistry (DFT calculations) to determine ion lifetimes and structures.

    • Main Results:

    • 4'-substituted-4-biphenylyloxenium ions were generated during hydrolysis.
    • Both first-order and second-order azide trapping were observed, with the latter occurring for short-lived ions.
    • Short-lived ions (1e, 1f) exhibit preassociation trapping mechanisms, distinct from diffusional trapping.
    • 4'-substituent effects on oxenium and nitrenium ion reactivity are similar in magnitude.

    Conclusions:

    • The lifetime of biphenylyloxenium ions dictates their trapping mechanism (diffusional vs. preassociation).
    • Short-lived ions necessitate preassociation, potentially via concerted S(N)2' or internal trapping mechanisms.
    • The electronic structure of these ions suggests a significant contribution from imino or oxo cyclohexadienyl carbocation character.