105864-93-5Relevant academic research and scientific papers
Electron Transfer Reactions in Organic Chemistry. IX. Acyoxylation and/or Debromodimerization Instead of Electron Transfer in the Reaction between Tris(4-bromophenyl)ammoniumyl and Aliphatic Carboxylates
Eberson, Lennart,Larsson, Berit
, p. 210 - 225 (2007/10/02)
The reaction between tris(4-bromophenyl)ammoniumyl tetrafluoroborate and carboxylate ions (acetate, pelargonate and t-butylcyanoacetate), in the form of their hydrogen dicarboxylate salts, was studied in acetonitrile by product and kinetic analysis.Contrary to an earlier proposal, single electron transfer is not observed.Instead, acyloxylation of the aryl group(s) is the preferred reaction mode around room temperature, whereas around 0 deg C, a competing process, debromodimerization of tris(4-bromophenyl)ammoniumyl, takes over.The latter reaction was not observed in dichloromethane.The mechanistic consequences of these findings for other applications of triarylammoniumyls as mediators and catalysts are briefly discussed.Also chloride ion reacted with tris(4-bromophenyl)ammoniumyl to give oxidative substitution products.
