Polarography of some coordination compounds of platinum. I. Hexammineplatinum (IV) and Tris(ethylenediamine)platinum(IV) ions

The polarographic reduction of tris(ethylenediamine)platinum(IV) and the hexammineplatinum(IV) ions has been studied in potassium chloride, potassium nitrate, and potassium nitrate plus ammonia solutions. Both ions were reduced irreversibly producing similarly shaped waves, showing well-defined diffusion current regions corresponding to two-electron reductions of the complexes. A linear relationship existed between diffusion current and concentration within the range examined. In aqueous potassium chloride and potassium nitrate media, the waves contained slight inflexions at positions corresponding to one-electron additions. The phenomenon suggested the transient presence of platinum(III) ions, and indicated that the half-wave potential of the reduction of the complexes to the trivalent state was very close to the half-wave potential of the reduction from platinum(IV) to platinum(II). The values were so close together as to indicate the improbability of isolating the trivalent complexes. Gelatin enhanced the inflexion in the wave but shifted the wave in a more negative direction. An increased concentration of supporting electrolyte also shifted the wave to a more negative position. In all cases a continuous discharge began at about -1.3 V (v. S.C.E.). This discharge was so far removed from that of the potassium ions of the supporting electrolyte that it was attributed to the discharge of hydrogen. Since the initial reduction of the platinum complexes corresponded to a two-electron change, it can be represented by reduction to a tetrammine ion. It is postulated that at higher applied potentials (namely, -1.3 V v. S.C.E.) the reduction proceeded further, producing platinum metal. This platinum metal would be in an active state, insoluble in mercury, and being on the surface, would lower the overvoltage of hydrogen leading to its discharge at a more positive potential than on a pure mercury surface. This view was supported by the fact that gas bubbles were observed at the dropping electrode when a voltage greater than -1.3 V was applied to the electrode for some time. When ammonia was added to the supporting electrolyte, a wave, without an inflexion, and corresponding to an irreversible two-electron reduction, was obtained at more negative potentials. The bivalent tetrammineplatinum(II) and bis(ethylenediamine)platinum(II) ions also gave polarograms showing the continuous discharge of hydrogen.