Solid-Phase Quasi-Intramolecular Redox Reaction of [Ag(NH3)2]MnO4: An Easy Way to Prepare Pure AgMnO2

Two monoclinic polymorphs of [Ag(NH3)(2)]MnO4 containing a unique coordination mode of permanganate ions were prepared, and the high-temperature polymorph was used as a precursor to synthesize pure AgMnO2. The hydrogen bonds between the permanganate ions and the hydrogen atoms of ammonia were detected by IR spectroscopy and single-crystal X-ray diffraction. Under thermal decomposition, these hydrogen bonds induced a solid-phase quasi-intramolecular redox reaction between the [Ag(NH3)(2)](+) cation and MnO4- anion even before losing the ammonia ligand or permanganate oxygen atom. The polymorphs decomposed into finely dispersed elementary silver, amorphous MnOx compounds, and H2O, N-2 and NO gases. Annealing the primary decomposition product at 573 K, the metallic silver reacted with the manganese oxides and resulted in the formation of amorphous silver manganese oxides, which started to crystallize only at 773 K and completely transformed into AgMnO2 at 873 K.

Automated summary

Two monoclinic polymorphs of [Ag(NH3)(2)]MnO4 containing a unique coordination mode of permanganate ions were prepared, with the high-temperature polymorph used as a precursor to synthesize pure AgMnO2. During thermal decomposition, the hydrogen bonds between permanganate ions and ammonia atoms induced a solid-phase quasi-intramolecular redox reaction, leading to the formation of finely dispersed elementary silver, amorphous MnOx compounds, and gases such as H2O, N-2, and NO. Subsequent annealing of the primary decomposition product resulted in the formation of amorphous silver manganese oxides, which transformed into AgMnO2 at higher temperatures.