When silver reacts with oxygen at 100–200° silver peroxide with a sodium chloride type cubic lattice is formed, most often with preferred orientation of the crystals. The high degree of symmetry of the lattice indicates that the peroxide ion is either in free rotation or in a state of torsional oscillation.
In the reaction with olefins the lattice is destroyed to form silver crystals, which sometimes have new textures.
The older views that it is possible to have silver peroxide, and that the oxygen is adsorbed in an atomic monolayer have got to be abandoned, since the Traub-Bach-Engler peroxide theory has turned out to be applicable to a silver catalyst too.
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Vol, Y.T., Shishakov, N.A. The nature of the selective action of a silver catalyst in soft oxidation reactions. Russ Chem Bull 11, 540–545 (1962). https://doi.org/10.1007/BF00904749