The Electroreduction of Beta-Aminoethyl Mercurials

Abstract

2‐(Piperidino)‐ethylmercuric chloride (I) and 2‐(diethylamino) ethylmercuric chloride (II) are each reduced by two separate one‐electron reductions in DMF or 50% ethanol. The products formed are the corresponding bis‐2‐ aminoethylmercury compound and/or the secondary amine (piperidine or diethylamine) depending on the solvent and reduction potential. Only traces of tertiary amine were detected. Bis[2‐(piperidino)‐ethyl] mercury (II) is reduced to piperidine in 50% ethanol, but no reduction occurs in DMF

Cyclic Voltammetry and Chronocoulometry with trans-Rh(en)[sub 2]Cl[sub 2]+] at Mercury Electrodes

“…Often this feature is preceded by the appearance of several, less prominent current peaks during the reductive half of the potential cycle. Such "wrong-way" current peaks in cyclic voltammograms have been previously reported in a variety of systems (16)(17)(18)(19), especially those involving the generation of free radicals capable of spontaneous reactions with mercury electrode surfaces to yield organomercurial products (16)(17)(18). Although we were usually able to find conditions (high scan rates, low concentrations) where these anomalies were absent, it seems worthwhile to report their prominence under other conditions and to express our concurrence with the suggestion ( 16) that their origin is related to that of polarographic maxima, namely convective stirring of the electrode-electrolyte interface (20).…”

“…The sudden changes in interracial tension usually associated with such stirring of the interracial region are accentuated by rapid changes in the concentrations of adsorbing species, Rh(en)2 + in the present case. The fact that the "wrong-way" current peaks appear at just the potentials where the chronocoulometric data show the greatest adsorption of Rh(en)2 + adds support to this interpretation, as does the similarity between the chemistry of organic radicals and Rh(en)2 +, both of which attack mercury electrodes to produce mercurated products (8,16,18).…”

“…The major anomalous feature in the voltammogram is the appearance of a reductive current peak during the oxidative half of the potential cycle. The fact that the "wrong-way" current peaks appear at just the potentials where the chronocoulometric data show the greatest adsorption of Rh(en)2 + adds support to this interpretation, as does the similarity between the chemistry of organic radicals and Rh(en)2 +, both of which attack mercury electrodes to produce mercurated products (8,16,18). Such "wrong-way" current peaks in cyclic voltammograms have been previously reported in a variety of systems (16)(17)(18)(19), especially those involving the generation of free radicals capable of spontaneous reactions with mercury electrode surfaces to yield organomercurial products (16)(17)(18).…”

Electrode reactions and electroanalysis of organomercury compounds

“…60 Under these conditions, the R 2 NCH 2 CH 2 Hg . radical partially dimerized and simultaneously reacted with the solvent 58 to afford hydride RHgH, which also decomposed to evolve ethylene Instability of such derivatives is well known, 164 namely, the rate constant for the reaction RHgH RH + Hg (20c) was from 0.02 (R = Me, Et) to 0.05 min 71 (R = Ph) and still higher in acidic media. 164 Obviously, this kind of reactions should compete, first of all, with steps (5) in Scheme 1, thus lowering the yield of R 2 Hg.…”

Organic polarography

“…Two waves were described for o-hydroxyphenylmercury chloride in aqueous HNO3 (789). Two 1-electron reduction steps were suggested for 2-(piperidino)ethylmercuric chloride and 2-(diethylamino)ethylmercuric chloride (1172).…”