Generation of Phenylmethylketyl Radicals in Aqueous Solutions
and Study of Their Transformation

A. G. Krivenko^z,a, V. A. Kurmaz ^a, A. S. Kotkin^a, G. V. Simbirtseva^b, and V. P. Gultyai^c

^a Institute of Problems in Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow oblast’, 142432 Russia

^b Chernogolovka Branch, Institute of Energy Problems in Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow oblast’, 142432 Russia

^c Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 117334 Russia

Received November 21, 2007

Abstract—Acetophenone and its intermediates formed upon the first electron transfer are studied by laser pho-
toemission and traditional electrochemistry. It is shown that the intermediate reduction is affected by com-
petition of the reactions of the formed radical-anions oxidation and their subsequent transformation to sec-
ondary products that are rapidly reduced at the electrode. From the comparison of the data obtained by the
laser photoemission method and electrochemical measurements a conclusion was drawn that the product is
a metastable complex (associate) of the radical-anion with water molecule; its formation rate constant is
rather low (~6 10³ M^–1 s^–1). It was also concluded that bulk radical reactions dominate in aprotic media at
moderate cathodic potentials; the acetophenone radical-anion is reduced at –1.9 V (SCE). This conclusion
agrees with the results of the acetophenone preparative electrolysis in DMFA, where marked yield of pinacon
was observed at the potentials of limiting current of the 1st reduction wave, while the stage of 2nd electron
transfer occurred at E 2.3 V (SCE).

Key words: intermediate, organic radicals, electroreduction, radical reactions, acetophenone

DOI: 10.1134/S1023193508120112

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