Kinetics and Mechanism of Silver(III) Reduction by Azide Ion in Aqueous Alkaline Media
Date of Original Version
The reaction between the tetrahydroxoargentate(III) ion and azide ion proceeds via formation of a monoazidosilver(III) complex, which undergoes internal two-electron redox only after reaction with an additional N3-. Formation of Ag(OH)3N3- from Ag(OH)4- and N3- obeys the full rate law for for reversible associative substitution by both solvent and ligand paths. Two parallel paths also occur in the redox step, both requiring adjacent azide groups prior to electron transfer. Final products are Ag(I) and N2. Three kinetic determinations of the equilibrium constant for Ag(OH)3N3- are in reasonable agreement with the value of 0.38 ± 0.14 obtained spectrophotometrically (25 °C, p = 1.2 M). The result that the nucleophilicity of N3- toward Ag(III) is slightly less than that of OH- is in agreement with previous observations for isoelectronic Pd(II). © 1984, American Chemical Society. All rights reserved.
Publication Title, e.g., Journal
Borish, Edward T., and Louis J. Kirschenbaum. "Kinetics and Mechanism of Silver(III) Reduction by Azide Ion in Aqueous Alkaline Media." Inorganic Chemistry 23, 15 (1984). doi: 10.1021/ic00183a028.