Mercury exchange reactions

Mercury compounds are often used as electrophiles in displacements on organomercurials. There are five possible combinations of reactants in such mercury exchange reactions. A dialkylmercurial substrate may be attacked either by a mercury salt (Reaction 4.43) or by a monoalkylmercurial (Reaction 4.44) and likewise a monoalkylmercurial may react either with a mercury salt or with another monoalkylmercurial (Reactions 4.45 and 4.46). Finally, a dialkylmercurial may react with another dialkylmercurial (Reaction 4.47). (In Reactions 4.43-4.47 and in other reactions in this section, one of the reactants, and the fragments derived from that reactant in the products, are written in italics. This is done to make it easier to follow the course of the reaction.)... 

We shall only discuss experiments that shed light on the first three types (Reactions 4.43-4.45), but the characteristics of all five types of mercury exchange reactions seem to be very similar. 

The first detailed study of the stereochemistry of a mercury exchange reaction that was known to be bimolecular was carried out as follows.83 Di-j-butyl-mercury was prepared by reacting optically active j-butylmercuric bromide with racemic i-butylmagnesium bromide as shown in Equation 4.48. 

Since the mercury-carbon bond is not disturbed in any way in this reaction, one (and only one) of the 5-butyl groups in the di-5-butylmercury should have an optically active center. The mercury exchange reaction of Equation 4.49 was then carried out on the di-j-butylmercury thus formed, and the optical rotation... 

The specific rotation of the initial. y-butyl bromide used by Charman, Hughes, and Ingold was —15.2°. The specific rotation of the product of the mercury exchange reaction was exactly half that, — 7.6°. When mercuric acetate or mercuric nitrate was used as the cleaving salt, the products showed a specific rotation of —7.5° and —7.8°, respectively. Thus this electrophilic substitution clearly proceeds with retention of configuration. 

Stereochemical studies on other mercury exchange reactions have been carried out, and all point to retention as the predominant pathway.84... 

Fig. 2. A possible reaction path and energy profile for the two-alkyl mercury-for-mercury exchange reaction.

Thus, not only should alkylmercuric iodides and dialkylmercurials have a more nucleophilic carbon compared with the others, but their respective -Hg-X functions should also be better leaving groups in electrophilic substitution reactions. This latter prophesy is supported in part by the results of Hughes et al. from their kinetic studies of mercury exchange reactions (20). 

Alkynyl anions are more stable = 22) than the more saturated alkyl or alkenyl anions (p/Tj = 40-45). They may be obtained directly from terminal acetylenes by treatment with strong base, e.g. sodium amide (pA, of NH 35). Frequently magnesium acetylides are made in proton-metal exchange reactions with more reactive Grignard reagents. Copper and mercury acetylides are formed directly from the corresponding metal acetates and acetylenes under neutral conditions (G.E. Coates, 1977 R.P. Houghton, 1979). 

An exchange reaction between bis(trifluorometbyl)mercury and tetrame-thylleud gives trimethyl(mfluoromethyl)plumbane [23] (equation 17) This plum-bane can also be prepared via the reaction of tetramethyllead with tnfluoromethyl radicals produced in a radio-frequency discharge of C2F [24]... 

Ligand exchange reactions can be used to prepare perfluoroalkylzinc compounds Solvated trifluoromethylzinc compounds can be synthesized via the reaction of dialkylzincs with bis(trifluoromethyl)mercury [36] (equation 27) A similar exchange process with bis(trif]uorometliyl)cadinium and diraethylzinc gives a mixture of tnfluoromethylcadmium and zinc compounds [77]... 

These compounds are the most stable of the three classes of organothal-lium(III) derivatives and have been prepared by a wide variety of classical organometallic procedures. Many exchange reactions of TIX3 (X = Cl, carboxylate) with organo derivatives of boron, mercury, tin, lead, etc., have been shown to result in formation of R2TIX compounds 73, 78), but are of relatively little preparative significance. The most frequently used procedure... 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

The mercuration of phosphonium derivatives has also been observed. The methylene group of the dimeric palladium complex 63 substituted by a carbonyl and a phosphonium functionality is readily mercurated upon reaction with Hg(OAc)2 to afford complex 64 (Equation (22)).7 Further studies demonstrated that the presence of a triphenylphosphonium group alone is sufficient to promote proton-mercury exchange. For example, the reaction of... 

Ion-exchange reactions were used for the accumulation of europium(III) [158] and iron(III) [159] ions on the surface of GCE coated with Nafion , and chromium(VI) ions on the surface of GCE covered by a pyridine-functionalized sol-gel film [160], which were combined with the stripping SWV Furthermore, a cathodic stripping SWV was used for the determination of sulfide [161,162], thiols [163-166], selenium(lV) [167-170], halides [171-173] and arsenic [174] accumulated on the snrface of mercury electrode. 

The dilithiated vinyllithium compound 1,2-dilithioethylene (132) was synthesized by Maercker and coworkers, using the mercury-lithium exchange reaction . Bis(chloromercurio)ethylene (131) was reacted with four equivalents of f-butyllithium... 

There are several useful means for preparation of organomercury compounds. The general metal-metal exchange reaction between mercury(II) salts and organolithium or magnesium compounds is applicable. The oxymercuration reaction discussed in Section... 

Solvated trifluoromethylzinc has also been prepared by ligand exchange reaction of dialkylzincs with bis(trifluoromethyl)mercury or cadmium (equation 2)110,11. Varying the reactant ratios led to mixed alkylperfluoroalkylzincs. 

Ligand exchange reactions have been used to prepare mercury(II) trialkylarsine complexes.202 Reaction of AgN03-AsMe3 with mercury halides gave the mercury arsine and silver halide (equations 10 and 11). The silver nitrate complex was not characterized. 

These results show that the palladium exchange reaction takes place predominately with retention of configuration at the carbon bearing the mercury. 

The hydration reaction of alkynes leading to carbonyl compounds is generally carried out in dilute acidic conditions with mercuric 1on salts (often the sulfate) as catalysts (ref. 5). Only very reactive alkynes (phenylacety-lene and derivatives) can be hydrated in strong acidic conditions (HgSO ) without mercury salts (ref. 6). Mercury exchanged or impregnated sulfonic resins have also been used in such reactions (ref. 7). Nevertheless, the loss of the catalyst during the reaction and environmental problems due to the use of mercury make this reaction method not as convenient as it should be for the preparation of carbonyl compounds. 

The importance of gas phase exchange reactions of the type HgA + AHg A1 IgA + Hg should also be determined. This could be assessed from the effect which the change of the isotopic composition of mercury vapor in the. absorbing enclosure lias upon the values of product enrichments. 

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