Mercury alkyl

Magnesium haUde and alkyl magnesium haUde precipitate and the alkyl magnesium compound remains in solution. Filtration (qv) followed by drying the filtrate yields soHd magnesium alkyl (11). Another preparation method is that of metal exchange using mercury alkyl in ether. 

Manganese cyclopentadienyl tricarbonyl (as Mn) Marble/calcium carbonate Mercury (alkyl compounds) (as Hg)... 

Many organometallic compounds are best prepared by this reaction, which involves replacement of a metal in an organometallic compound by another metal. The compound RM can be successfully prepared only when M is above M in the electromotive series, unless some other way is found to shift the equilibrium. That is, RM is usually an unreactive compound and M is a metal more active than M. Most often, RM is R2Hg, since mercury alkyls are easy to prepare and mercury is far down in the electromotive series." Alkyls of Li, Na, K, Be, Mg, Al, Ga, Zn, Cd, Te, Sn, and so on have been prepared this way. An important advantage of this method over 12-36 is that it ensures that the organometallic compound will be prepared free of any possible halide. This method can be used for the isolation of solid sodium and potassium alkyls." If the metals lie too close together in the series, it may not be... 

Work on mercury alkyls has been done by Heitz and Adloff (31-33), who studied Hg(CH3)2, Hg(C2Hj)2 and HgPh2. They found no isotope effect between " Hg, Hg, and ° Hg, and no correlation with the respective conversion coefficients. They also noted that the retentions could not be satisfactorily explained by exchange of the respective ligands, and thus concluded that the molecules are reformed by an epithermal not by a thermal process. Parent yields were typically 74, 15, and 8% for the diphenyl-, dimethyl- and diethylmercury, respectively. 

Mercury alkyls can be prepared by an analogous reaction in which an amalgam of sodium and mercury is used. 

For this process, suitable solvents include hydrocarbons, benzene, and ether. Lithium alkyls can also be prepared by the reaction of the metal with a mercury alkyl,... 

The overall process given by reaction (1) and reaction (2) is common to all mechanisms proposed for the decomposition of this alkyl. Whether this process occurs as written or by the simultaneous release of both methyl radicals is uncertain. Gowenlock et al.66 tried to resolve this problem and the similar problem that arises with other mercury alkyls by determining D(RHg-R) [R = CH3, C2H5, (CH3)2CH, CH3CH2CH2CH2] from appearance potential measurements. 

Fluorinated alkyl groups (Rp) can be radically attached to Ggp, for example by reaction of mercury-alkyl compounds under irradiation [10, 24] or by reaction with fluorinated alkyl iodides or bromides [25, 26]. Photochemical reaction with (R3Sn)2 or thermal reaction with RjSnH generates the Rp radical from the corresponding iodides or bromides. 

Several organolithium compounds have important apphcations in organic syntheses. These may be readily synthesized by reactions of lithium with organics. The metal reacts with alkyl or aryl halides or mercury alkyls or aryls to produce alkyl or aryl hthium. Some examples are ... 

Action of Grignard reagent on mercury(ll) chloride yields mercury alkyls ... 

Mercury alkyls are readily obtained by the actions of Grignard reagents (magnesium alkyl halides) on mercury(II) chloride. Thus, mercury dimethyl is made from magnesium methyl chloride and mercury(II) chloride ... 

Snell et al, "Colorimetric Methods of Analysis," vol IIA, Van Nostrand(1959), 156-87 Aluminum Alkyls were prepd in 1865 hy the action of aluminum on mercury alkyls(Refs 1 6)(see also Note below). Later they were made by the action of "electron metal (alloy of Al and Mg) on a sola of the alkyl halide in ether (Refs 2 6). The Al trialkyU are volatile liquids, violently attacked by air or water. Following are examples trimethylaluminum A1(CHS), d 0.752 at 20°/4°, mp 15.0°, bp 126. la, tri-ethyl-, Al(CaH5) d 0.837 at 20°/4°, mp -52.5°, bp 185.6a, tri-n-propyl-, Al(n-CjH,),. d 0.823 at 20°/4°, mp -107°, bp ca 250° (Refs 3,4,5 6). These three compds are inflammable in air and for this reason may be of interest as components of liquid propellants for rockets Note The prepn of a compd called "Aethyl-aluminium" was claimed by W.Hallwachs A.Schaffarik, Ann 109, 207(1859) hut it was not properly identified and its props (except that it is violently decomp by water) were not detd... 

A number of organometallic compounds show promise for LCEC study, and a few have already been examined in detail (especially mercury alkyls) [9]. More highly conjugated organic compounds such as a,a-unsaturated ketones and imines are occasionally good candidates, but at this time UV detectors frequently outperform electrochemical detectors for such systems. At this writing there have been only a few reported LCEC studies of metal ions or metal complexes. Perhaps the major reason for this is that very little modern LC has been carried out on them using any detector. It is difficult to compete with atomic spectroscopy techniques for the determination of most elements, but as speciation becomes more important, it seems likely that more LCEC methods will be developed for metal complexes. 

Snell et al, "Colorimetric Methods of Analysis," vol II A, Van Nostrand(1959), 156-87 Aluminum Alkyls were prepd in 1865 by tbe action of aluminum on mercury alkyls(Refs 1 6)(see also Note below). Later they were made by the action of "electron metal (alloy of Al and Mg) on a soln of the alkyl halide in ether (Refs 2 6). The Al trialkyls are volatile liquids, violently attacked by air or water. 

Beryllium dialkyls BeR2 are best made by one of the most general preparative methods for organometallics, by heating elemental beryllium with the corresponding mercury alkyl HgR2 ... 

The photooxidation of mercury alkyls is difficult to elucidate in that complicating reactions of mercury and the alkyl compounds themselves tend to obscure the simple oxidation of alkyl radicals. Martin and Noyes00 found that with mercury dimethyl they did not find formaldehyde to be a principal product of the photooxidation above 100°C. The reason is not obvious, but probably reflects the unsatisfactory nature of mercury dialkyls for studying the oxidation of alkyl radicals. 

Organoaluminum compounds, particularly AlEt3, are commercially very important as activators for olefin polymerization catalysts and are produced on a large scale, in spite of their pyrophoric nature and violent reaction with water. In the laboratory organoaluminum compounds can be made from mercury alkyls by transmetallation ... 

---