Electrochemistry of diazonium salts. Pathways of electrochemically initiated polymerization processes

The electrochemical reduction of several diazonium cations was examined on drop and stationary Hg-electrodes immersed in 1 M NaClO4 background electro lyte and water, acetone or water-acetone mixtures. Features of ongoing proc esses were investigated at various reduction potentials and in the presence of acrylamide as a radical scavenger. The products of electrochemical redu ction are mainly polymeric substances containing hydrogen, carbon and nitro gen. The polymerization pathways were discovered on the basis of a thorough analysis of thermochemical data obtained at the level of the semiempirical PM3 method and statistical thermodynamics. Possible applications of the el ectrochemical reduction of diazonium cations as polymerization (polycondens ation) initiators are suggested.