Abstract: | It has been established that the process of splitting of the P-P bonds of the white phosphorus molecules is initiated by cathode-generated nucleophiles (HO–, RO–), while functionalization of the P-H bond formed in phosphoric oligomers occurs under the action only of alcohol. The primary product after splitting of all the P-P bonds in phosphoric oligomers is dialkylphosphite (in alcohol-water media), or trialkylphosphite (in absolute alcohol), in the course of electrolysis being transformed into trialkylphosphate. Formation of esters of pyrophosphoric acid with reduced protogenic character of the medium was examined. It is proposed that under these conditions nucleophilic reagents of the type (P)c-O– form and participate in splitting of the P-P bonds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences, 420083 Kazan. V. I. Ul'yanov-Lenin State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2033–2038, September, 1992. |