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

• Published in: Journal of fluorine chemistry Vol. 103; no. 1; pp. 85 - 91
• Main Authors: Shaposhnikova, E.N., Sterlin, S.R., Solodovnikov, S.P., Bubnov, N.N., Tumanskii, B.L.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.04.2000; Elsevier
• Subjects: Anion–radical; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; EPR; Perfluoroalkyl α-triketones; Physical Sciences; Radical pairs; Reduction; Science & Technology; Reduction; Radical pairs; Anion–radical; EPR; Perfluoroalkyl α-triketones; anion-radical; ESR; REACTIVITY; radical pairs; perfluoroalkyl alpha-triketones; reduction
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/S0022-1139(99)00258-4

Reaction of α,β-bis-fluorosulfatoketones i-C 3F 7(CFOSO 2F) 2C(O)R F, (R F=C 2F 5, i-C 3F 7) with AcONa/AcOH afforded perfluoro-α-triketones i-C 3F 7C(O)C(O)C(O)R F, (R F=C 2F 5, i-C 3F 7). 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.