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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Systematic repression of beta-silyl carbocation stabilization.

Xavier Creary1, Elizabeth D Kochly

  • 1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA. creary.1@nd.edu

The Journal of Organic Chemistry
|February 11, 2009
PubMed
Summary
This summary is machine-generated.

The beta-trimethylsilyl group significantly enhances solvolysis rates, but this effect is diminished in cyclopropyl and benzocyclobutyl systems due to structural constraints and antiaromaticity. Computational studies confirm these findings, though they may overestimate stabilization.

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Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Computational Chemistry

Background:

  • The influence of silicon substituents on carbocation stability is a key area in organic chemistry.
  • Understanding reaction mechanisms, particularly solvolysis, provides insights into electronic effects and transition states.

Purpose of the Study:

  • To investigate the effect of beta-trimethylsilyl groups on the solvolysis rates of cyclopropyl and benzocyclobutyl systems.
  • To compare experimental solvolysis data with computational predictions of carbocation stabilization.

Main Methods:

  • Solvolysis reactions of substituted cyclopropyl and benzocyclobutyl derivatives.
  • Density Functional Theory (DFT) calculations (B3LYP/6-31G*) to model carbocation stabilization energies.

Main Results:

  • A rate enhancement of approximately 10^6 was observed for 1-(trimethylsilylmethyl)cyclopropyl mesylate solvolysis.
  • Solvolysis of 1-phenyl-2-trimethylsilylcyclopropyl chlorides showed 10^3-10^4 rate enhancements.
  • Beta-silyl stabilization was significantly reduced in benzocyclobutyl systems (3.7 kcal/mol) compared to cyclopropyl systems (12-16.6 kcal/mol).

Conclusions:

  • The beta-trimethylsilyl group's stabilizing effect on carbocations is context-dependent, being repressed in strained ring systems.
  • Computational studies generally align with experimental solvolysis trends but can overestimate stabilization.
  • Antiaromaticity plays a role in diminishing beta-silyl stabilization in benzocyclobutenyl carbocations.