Mercury compounds dissolving metal reductions

In reductive acylation and dimerization, the cathode is often superior to dissolving metal or radical anions reductants. So a, j6-unsaturated ketones or esters can be acylated in high yield to 1,4-dicarbonyl compounds at the mercury cathode [39], but the corresponding reaction with sodium in tetrahydrofuran (THE) fails [40]. On the other hand, reductive acylation of double bonds becomes possible in high yield, when vitamin Bj2 is used as mediator [41]. Here cobalt-alkyl complexes play a decisive role as intermediates. 

Adsorptive accumulation — Organic substances which exhibit -> surface activity and electroactivity can be electrochemically analyzed by adsorptive accumulation on the surface of a an electrode, e.g., mercury electrode, followed by the reduction, or oxidation of the adsorbate using -> voltammetry [i,ii]. Also, the adsorption of highly stable and inert -> complexes of metal ions with surface-active organic ligands is utilized for the determination of trace metals [iii]. In all these methods the maximum voltammetric response is linearly proportional to the surface concentration of the adsorbed analyte at the end of the accumulation period [iv]. In the majority of cases, the adsorption on mercury can be described by the -> Frumkin isotherm /icx=o = 0exp(ad)/(1- 9), where f is the adsorption constant, cx=o is the concentration of the dissolved compound at the electrode surface, 6 = T/rmax is the surface coverage, T is the surface concentration of the adsorbed compound, rmax is the maximum surface concentration and a is the Frumkin... 

Carbonyl platinum dichloride has a distinctly basic character. It dissolves in excess of hydrochloric acid to a lemon-yellow solution, due, perhaps, to the formation of a soluble hydrochloride, PtCl2.CO.HCl. This solution is a powerful reducing agent, effecting the reduction of silver, gdld, and mercury from their salts.1 The monocarbonyl unites with soluble metallic chlorides, such as those of the alkali metals, to yield yellow, crystalline double salts. These, however, are so readily soluble and so easily decomposed that their satisfactory isolation has proved difficult. With the chlorides of certain organic bases, however, well-defined compounds have been obtained.4... 

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