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Related Experiment Videos

Should dithiophosphinate esters function as RAFT agents?

Jennifer L Hodgson1, Katy A Green, Michelle L Coote

  • 1ARC Centre of Excellence in Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia.

Organic Letters
|October 8, 2005
PubMed
Summary

Methyl radical addition to dithiophosphinate esters is less exothermic than to RAFT agents, limiting their use in polymerization but favoring their role as radical chain carriers in synthesis.

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Area of Science:

  • Computational Chemistry
  • Polymer Science
  • Organic Synthesis

Background:

  • Reversible-Deactivation Radical Polymerization (RDRP) techniques are crucial for polymer synthesis.
  • RAFT (Reversible Addition-Fragmentation chain Transfer) agents are widely used in RDRP.
  • Dithiophosphinate esters are analogous compounds to RAFT agents, with potential applications in radical chemistry.

Purpose of the Study:

  • To investigate the reactivity of dithiophosphinate esters towards radical addition.
  • To compare the stability of phosphoranyl radicals with carbon-centered radicals.
  • To evaluate the potential of dithiophosphinate esters in controlling free-radical polymerization and as radical chain carriers.

Main Methods:

  • High-level ab initio calculations were employed.

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  • The study focused on the addition of the *CH3 radical to the sulfur center of dithiophosphinate esters S=P(Z)(Z')SCH3.
  • Reactivity was compared with addition to analogous RAFT agents S=C(Z)SCH3.

    • Main Results:

    • Methyl radical addition to dithiophosphinate esters was found to be considerably less exothermic than to RAFT agents.
    • This indicates a lower propensity for dithiophosphinate esters to act as effective RDRP agents.
    • The calculations suggest that phosphoranyl radicals may not be as intrinsically stabilized as previously thought compared to carbon-centered radicals.

    Conclusions:

    • Dithiophosphinate esters are likely to have limited utility in controlling free-radical polymerization.
    • These compounds show promise as effective radical chain carriers in organic synthesis.
    • The study challenges the established understanding of phosphoranyl radical stability relative to carbon-centered radicals.