EPR studies of anion–radicals formed by reduction of perfluorinated α-triketones with some metals of groups I–III

Reaction of α,β-bis-fluorosulfatoketones i-C3F7(CFOSO2F)2C(O)RF, (RF=C2F5, i-C3F7) with AcONa/AcOH afforded perfluoro-α-triketones i-C3F7C(O)C(O)C(O)RF, (RF=C2F5, i-C3F7). Reduction of these triketones with metals (Li, Na, K, Mg, Cd, Zn, Tl) in THF was studied by EPR spectroscopy. Anion–radicals with unsymmetrical distribution of charge and spin densities are formed in one-electron reduction of the triketones. Unlike hydrocarbon α-polyketones, perfluorinated triketones can undergo three-electron reduction to form paramagnetic allyl tisalkoxides.