Formation of diazohydroxides ArN 2 OH in aqueous acid solution: polarographic determination of the equilibrium constant K R for the reaction of 4-substituted arenediazonium ions with H 2 O †
In aqueous acid (pH <4) solutions, in the dark, and in the absence of reductants, arenediazonium ions, ArN 2 + decompose spontaneously through the rate-limiting formation of the extremely unstable aryl cation that reacts with any nucleophile present in its solvation shell (D N + A N mechanism). However, in weak acidic and alkaline solutions, + to determine, for the first time, the equilibrium constants K R of formation of 4-substituted X-ArN 2 OH (X¼H, Me, MeO, Br, and NO 2 ), which can decompose in several ways including Z-E isomerization or further reaction with OH À to give diazoate ArN 2 O À . The technique applied was differential pulse polarography, which is very selective and sensitive. The determined pK R values are 5-6, and they are somewhat higher than those obtained for the reaction of ArN 2 + with alcohols ROH (pK DE = 3-5) under similar acidic conditions. The K R values are not very sensitive to changes in the nature of the substituent in the aromatic ring and a linear Hammett plot with a slope of ρ = 0.58 was obtained
