A survey of the reaction of the coordinated nitrite ions of the nitro-ammine-Co (III) complexes.

Abstract

Both the reduction and the oxidation of the nitrite of the nitro-ammine-cobalt(III) complexes are much slower than that of the free nitrite. In general there is a parallelism between the rate of aquation of the complex and the rate of the redox reaction of the coordinated nitrite. In oxidation reactions there is no detectable intermediate. Oxidizing the mononitro complex the original valence state of the central cobalt(III) ion is preserved, with other complexes a gradual reduction of the central ion occurs. In reduction reactions more or less stable intermediates can be detected. With azide ion the intermediate is not identical with that of the reaction of the azidopentaamminecobalt (III) complex with nitrate. The coordinated ligands act on the reactivity of a particular ligand either through their effect on the electron distribution of the whole complex or by means of a direct chemical interaction between adjacent ligands.