Chemical and Electrochemical Oxidation of Solutions of Silver Nitrate in Acetonitrile

Article abstract of DOI:10.1021/j100253a038

In anhydrous acetonitrile the unstable, brown species Ag(NO3)4^2-, I, can be produced either by the electrolysis of silver nitrate or by the equilibrium reaction N2O5 + Ag⁺ + 3NO3^- ->/<- I + NO2, for which the concentration quotient is 8.0 M^-3.The ESR spectrum of I at 77 K is that of a Ag(II) ion in a field with pronounced axial distortion.Its resonance Raman spectrum indicates square-planar coordination of the metal ion by unidentate nitrate ligands.The complex decomposes to form cyanomethyl nitrate and nitric acid by the rate law -d/dt = k/->.In the presence of p-xylene a major organic product is p-methylbenzyl nitrate.Equilibrium and electrochemical studies lead to estimated ΔG⁰₂₉₈ values for the free radical and ionic dissociation pathways of N2O5 in acetonitrile solution of +38 and -26 kJ, respectively.