Free Radical Processes in the Reactions of Organometallics with Organic Sulfur Compounds

  • Glen A. Russell
  • Preecha Ngoviwatchai
Part of the NATO ASI Series book series (NSSA, volume 197)


Sulfur-centered radicals, RSO n with n = 0 or 2 and presumably 1, react readily with certain organometallic reagents to generate alkyl radicals. These reactions can involve a formal SH2 substitution at a metal atom such as Li or Hg,1–3 e.g., reaction 1, or electron transfer with an easily oxidized organometallic species, reaction 2.3 The rates of reactions 1 and 2
$$RSO_{n}^{\bullet }+{{R}^{1}}HgCl\to RS{{O}_{n}}HgX+{{R}^{1\bullet }}$$
$$RSO_{n}^{\bullet }+{{\left( {{R}^{1}} \right)}_{2}}C{{u}^{-}}\to RSO_{n}^{-}+{{R}^{1\bullet }}+{{R}^{1}}Cu$$
increase at least qualitatively with the electrophilicity of the attacking radical and with the stability of the alkyl radical formed. Thus, reaction I occurs slowly when the attacking radical is a nucleophilic alkyl radical, such as t-Bu or t-BuCH2CHSPh, but readily with electrophilic species such as t-BuCH2CHSO2Ph or heteroatom-centered radicals including PhSO n or halogen atoms.


Relative Reactivity Competitive Reaction Organic Sulfur Compound Nucleophilic Radical Phenyl Sulfone 
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Copyright information

© Plenum Press, New York 1990

Authors and Affiliations

  • Glen A. Russell
    • 1
  • Preecha Ngoviwatchai
    • 1
  1. 1.Department of ChemistryIowa State UniversityAmesUSA

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