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Does metal ion complexation make radical clocks run fast?

Anselm H C Horn1, Timothy Clark

  • 1Computer-Chemie-Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstrasse 25, 91052 Erlangen, Germany.

Journal of the American Chemical Society
|February 27, 2003
PubMed
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Metal cations significantly lower the ring-closure barrier in radical clock reactions. This effect, observed computationally for various ions like lithium, is also relevant in solution, impacting reaction rates.

Area of Science:

  • Computational Chemistry
  • Physical Organic Chemistry
  • Reaction Mechanism Studies

Background:

  • Radical clock reactions are crucial for measuring radical reaction rates.
  • The 1-hexen-6-yl radical cyclization is a well-studied example.
  • Understanding factors influencing the cyclization barrier is key to refining kinetic measurements.

Purpose of the Study:

  • To investigate the effect of metal cation complexation on the ring-closure barrier of the 1-hexen-6-yl radical.
  • To computationally assess the influence of various monovalent metal cations (Li+, Na+, K+, Cu+, Ag+) on this radical clock reaction.
  • To explore the potential significance of this effect in both gas-phase and solution-phase reactions.

Main Methods:

  • Ab initio molecular orbital and density functional theory (DFT) calculations were employed.

Related Experiment Videos

  • Specific computational levels used include CBS-RAD(QCISD,B3-LYP) for Li+ and B3LYP for other cations.
  • Explicit solvation models (using tetrahydrofuran) were included for lithium ion complexation studies.

    • Main Results:

    • Complexation of the double bond to metal cations significantly decreases the ring-closure barrier of the 1-hexen-6-yl radical.
    • This barrier lowering effect was consistently observed across all calculated monovalent cations (Li+, Na+, K+, Cu+, Ag+).
    • Calculations including explicit solvation suggest the effect is also present in solution, not just the gas phase.

    Conclusions:

    • Metal cation complexation is a potent modulator of radical clock reaction rates.
    • The observed barrier lowering by metal ions has implications for the design and interpretation of experimental radical clock studies.
    • The findings suggest that solvation effects do not negate the influence of metal cations on radical cyclization barriers.