Reductants mercury

Scheme 9. Danishefsky s synthesis of bicyclo[3.3.0]octane 52 using Giese s reductive mercury method.

Bacterial mercuric reductase is a unique metal-detoxification biocatalyst, reducing mercury(II) salts to the metal. The enzyme contains flavin adenine dinucleotide, a reducible active site disulfide (Cys 135, Cys i4o), and a C-terminal pair of cysteines (Cys 553, Cys 559). Mutagenesis studies have shown that all four cysteines are required for efficient mercury(II) reduction. Mercury Lm-EXAFS studies for mercury(II) bound to both the wild-type enzyme and a very low-activity C-terminal double-alanine mutant (Cys 135, Cys uo, Ala 553, Ala 559) suggest the formation of an Hg(Cys)2 complex in each case (39). The Hg—S distances obtained were 2.31 A and are consistent with the correlation of bond length with coordination number presented above. Thus, no evidence was obtained for coordination of mercury(II) by all four active-site cysteines in the wild-type mercuric reductase. However, these studies do not define the full extent of the catalytic mechanism for mercury(II) reduction, and it is possible that a three- or four-coordinate Hg(Cys) complex is a key intermediate in the process. 

An analysis of literature results allows one to divide the metallic electrode materials into two groups. The first involves electrodes on which the O2 reduction proceeds predominantly through intermediate hydrogen peroxide formation while the second involves parallel mechanisms (i.e., both the four-electron and two-electron reductions). Mercury, pyrographite, " and other different types of the carbon materials,and are classified in the first group. 

Mercuric chloride test. Add mercuric chloride solution to formic acid or a solution of formate and w arm. A white precipitate of mercurous chloride, insoluble in dil. HCl, is produced. Sometimes the reduction proceeds as far as metallic mercury, which appears as a grey precipitate. 

A mechanical device embodying a bellows-sealed needle valve with a lever reduction movement for fine control is shown in Fig. II, 23, 5. The needle is of stainless steel. This fine control valve assembly is useful for pressures ranging from 20 to 100 mm. of mercury when used in conjunction with a good water pump. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

Acetamido-4-methylselenazole can react with mercuric acetate to yield 5-mercuriacetate derivatives that can be converted to the chloro derivatives by the action of sodium chloride. Treatment with potassium iodide leads to reduction regenerating the initial compound with loss of mercury (Scheme 16) (4). 

The most commonly used method for reducing an aryl ketone to an alkylbenzene employs a zinc-mercury amalgam m concentrated hydrochloric acid and is called the Clemmensen reduction Zinc is the reducing agent... 

Controlled-potential coulometry also can be applied to the quantitative analysis of organic compounds, although the number of applications is significantly less than that for inorganic analytes. One example is the six-electron reduction of a nitro group, -NO2, to a primary amine, -NH2, at a mercury electrode. Solutions of picric acid, for instance, can be analyzed by reducing to triaminophenol. 

Other volatile compounds of elements can be used to transport samples into the plasma flame. For example, hydride reduction of mercury compounds gives the element (Hg), which is very volatile. Osmium can be oxidized to its volatile tetroxide (OSO4), and some elements can be measured as their volatile acetylacetonate (acac) derivatives, as with Zn(acac)2. 

AppHcations of mercury include use in batteries (qv), chlorine and caustic soda manufacture (see Alkali and chlorine products), pigments (see Pigments, inorganic), light switches, electric lighting, thermostats, dental repair (see Dental materials), and preservative formulations for paints (qv) (1—3). As of the end of the twentieth century, however, increased awareness of and concern for mercury toxicity has resulted in both voluntary and regulatory reduction of mercury usage (see also Mercury compounds). 

Electrode reduction potentials of mercury are given in Table 4. 

Batteries. Many batteries intended for household use contain mercury or mercury compounds. In the form of red mercuric oxide [21908-53-2] mercury is the cathode material in the mercury—cadmium, mercury—indium—bismuth, and mercury—zinc batteries. In all other mercury batteries, the mercury is amalgamated with the zinc [7440-66-6] anode to deter corrosion and inhibit hydrogen build-up that can cause cell mpture and fire. Discarded batteries represent a primary source of mercury for release into the environment. This industry has been under intense pressure to reduce the amounts of mercury in batteries. Although battery sales have increased greatly, the battery industry has aimounced that reduction in mercury content of batteries has been made and further reductions are expected (3). In fact, by 1992, the battery industry had lowered the mercury content of batteries to 0.025 wt % (3). Use of mercury in film pack batteries for instant cameras was reportedly discontinued in 1988 (3). 

Environmental Factors. The control, recovery, and disposal of mercury-bearing waste products are as important to the mercurials industry as the manufacturing process. The difficulties involved in removing mercury from waste-product streams and the problems of recovery or disposal have resulted in a substantial reduction in the number of manufacturers of mercury compounds as well as in the variety of mercury compounds being manufactured. Moreover, the manufacturing process used for a mercury compound may not necessarily be the most efficient or economical. Rather, the choice may depend on the nature of the by-products, the toxic hazard of the process, and the ease of recovery of the mercury from the waste-product stream. 

Reduction to Gaseous Metal. Volatile metals can be reduced and easily and completely separated from the residue before being condensed to a hquid or a soHd product in a container physically separated from the reduction reactor. Reduction to gaseous metal is possible for 2inc, mercury, cadmium, and the alkah and aLkaline-earth metals, but industrial practice is significant only for 2inc, mercury, magnesium, and calcium. 

Neta.1 Ama.lga.ms. Alkali metal amalgams function in a manner similar to a mercury cathode in an electrochemical reaction (63). However, it is more difficult to control the reducing power of an amalgam. In the reduction of nitro compounds with an NH4(Hg) amalgam, a variety of products are possible. Aliphatic nitro compounds are reduced to the hydroxylamines, whereas aromatic nitro compounds can give amino, hydra2o, a2o, or a2oxy compounds. 

In removing excess free chlorine from municipal or industrial water and from wastewater, sodium sulfite competes with bisulfite or sulfur dioxide. Other commercial appHcations of sodium sulfite in wastewater treatment include the reduction of hexavalent chromium to the less toxic Cr " salts as well as the precipitation of silver and mercury. 

Electrolytic reduction with a mercury or platinum electrode produces equimolar amounts of sulfide and sulfite ... 

Titanium diiodide may be prepared by direct combination of the elements, the reaction mixture being heated to 440°C to remove the tri- and tetraiodides (145). It can also be made by either reaction of soHd potassium iodide with titanium tetrachloride or reduction of Til with silver or mercury. 

---