A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate

The reaction of ammoniacal AgNO3 solution (or aq. [Ag(NH3)2]NO3) with NaClO4 resulted in [Ag(NH3)2]ClO4 (compound 1). Detailed spectroscopic (correlation analysis, IR, Raman, and UV) analyses were performed on [Ag(NH3)2]ClO4. temperature enthalpy phase change for compound 1 determined to be 225.7 K 103.04 kJ/mol, respectively. We found the thermal decomposition involves a solid-phase quasi-intramolecular redox between perchlorate anion ammonia ligand, resulting lower valence chlorine oxyacid (chlorite, chlorate) components. did not detect loss during formation AgClO4. However, ion intermediates containing chlorate/chlorite, which disproportionated (either solid or aqueous solutions after dissolution these water) into AgCl silver perchlorate. propose that AgCl-AgClO4 mixture eutectically melts, AgClO4 decomposes this melt O2. Thus, final product is AgCl, N2, H2O. intermediate phases identified by XPS, titrimetric methods.