Studies on the transients generated in the γ radiolysis of benzoyl-1,1,1-trifluoroacetone in glassy matrices: the radiolytically induced ketonization

Abstract

The transients generated in the γ radiolysis of deaerated solutions of benzoyl-1,1,1-trifluoroacetone (BTA) are stabilized at 77 K and studied by their absorption spectra in the glassy matrices of isopropyl alcohol and methanol-11 mol % H₂O. The transients identified are BTA_enol, BTA_keto, BTAH√ _ketyl, [BTA^2-_enolate]_unrelax, and [BTA^2-_enolate]_{rela x}. BTA_enol isomerizes to BTA_keto, apparently suggesting that anion radical formation stabilizes the keto form. BTA^2-_enolate undergoes configurational relaxation from an initially unstable to a final stable relaxed configuration. Both BTA_enol and BTA_keto react with protons produced on γ radiolysis to give BTAH^√ _ketyl.