Diphenylmercury, reaction with

Diphenylmercury, reaction with aluminum to give tnphenylaluminum,... 

Subsequent kinetic work has amply confirmed the mechanistic picture described above. For example, the reaction of diphenylmercury with Ph(COOEt).CH.HgBr gives an almost instantaneous reaction with precipitation of phenylmercuric bromide, whereas reaction of the soluble product with a second molar equivalent of mercuric bromide gave a very slow (ca. 2 weeks) precipitation of phenylmercuric bromide722, i.e. reaction involves (287) and (288)... 

Diphenylmercury interacts with nickel supported on alumina, under H2 and in heptane solution, at 373 K, to give mostly biphenyl and metallic mercury. During the reaction, Hg induces leaching of nickel, which leads to a progressive deactivation of the catalyst (Scheme 2.42) [126]. 

Holliday and Taylor (59) have studied the reactions of tetrafluorodi-borane(4) with several organometallic reagents. No evidence was obtained for the formation of organo-substituted diboron compounds. Reaction with diphenylmercury led to reduction of a major fraction of the organometallic to metallic mercury, with formation of difluorophenylborane and BF3.Diethylmercury was reduced similarly, with formation of ethyldi-fluoroborane, BF3, and ethane. With tetravinyltin, the major products... 

The reactions in Eqs. 5.1 and 5.2 show two contrasting preparative reactions of triorganoaluminum. They are classihed into redox type and metal exchange type in Scheme 5.1, respectively. Diphenylmercury reacts with metallic aluminum to induce the transfer of the phenyl group from Hg to Al, producing AlPha and Hg (Eq. 5.1) [10]. 

Unlike (C6p5)2Hg, tiis(pentafluorophenyl)bismuth reacts with Yb very slowly at 55°C [9]. An attempt to isolate (C6F5)2Yb in this reaction has failed. Diphenylmercury does not react with common ytterbium [9], but does with ytterbium, which is activated by methyl iodide, to form Ph2Yb (according to the infra red spectrum of the reaction mixture and products of its reactions with H2O, PhjSnCl and 9-fluorenone) [16]. 

A further kinetic investigation of the rates of cleavage of diphenylmercury (and some dialkylmercurials) showed similar kinetic features608. The first-order rate for the reaction of diphenylmercury with acetic acid at 25 °C was 4.98 x 10", which agreed quite well with the value from the above determination (2 x 10-4 at 42 °C with dioxan). In the presence of perchloric acid, second-order kinetics were found to be obeyed (for dineophyl mercury and presumably for diarylmercurials as well) for a twofold concentration change in both mercurial and perchloric acid. Two separate mechanisms were proposed for the reactions in the absence, and presence, of perchloric acid. Under the former conditions an SEi process (244) was... 

Treatment of diphenylmercury with nitrosyl chloride produced some nitro-sobenzene [64]. The reaction of phenylmagnesium chloride with nitrosyl chloride also produced this compound [65], However, cyclohexylmagnesium... 

In addition to these quantitative results, there are a few purely qualitative statements regarding exchange reactions on mercury in the literature, e.g., bis(pentachlorophenyl)mercury with diphenylmercury or dimethylmercury has been found to yield the respective mixed compounds (228). 

This middle-range fraction was maximized by the addition of a little diphenylmercury at the beginning of the reaction. The reaction solution was again washed with water to deactivate any chlorine or sodium chain ends, dried, and refluxed with sodium, and HMDS was added. By analyzing for... 

Reactions of B2F4 with diphenylmercury and tetravinyltin have been mentioned previously (Section I,A). No evidence was obtained for addition to the double bonds of the organometallic reagent in these studies. 

The cleavage of diphenylmercury in acetic acid with perchloric acid, and the reaction of dialkylmer-cury with mercury nitrate, may be considered as exhibiting the pure 5e2 mechanism, where an attack of the electrophile at the metal-bonded C-atom is the rate-determining step. ... 

Pentaphenylantimony (7) and pentaphenylphosphorus (10) react with phe-nylmercuric chloride (8) to form (9) and (11) respectively with diphenylmercury as the byproduct. A similar but slightly more complex reaction occurs between (7) and ferrocenylmercuric chloride (C5H5FeC5H4HgCl). 

Along this same line the reaction of the 3-acetoxy irfo-5-norticyclyl bis(p3rridine) palladium with diphenylmercury gave the e (/o-3-phenyl-5-mercury derivative. This was postulated to proceed via attack of coordinated phenyl on the carbon-acetate bond (278) ... 

Preparation, (a) From diphenylmercury. Diphenylmercury, a highly toxic substance melting at 121-123°, is prepared by reaction of bromobenzene in xylene with 3% sodium amalgam. A mixture of this substance and zinc wool is refluxed... 

The reactions between dialkenyl- or diarylmercury derivatives and (ejco-5-acetoxy-tricyclo[2.2.1.0 ]hept-enmercury derivatives with an enrfo-5-alkenyl or an endo-S-aryX substituent, respectively. The best results were obtained in methanol much less satisfactory results were obtained in acetonitrile. Yields above 50% were obtained when diphenylmercury and bis(2-methylprop-l-enyl)mercury were employed giving 6 and 7, respectively. 

When the preparation of a halide-free diorganomagnesium compound is desired, the method of choice is the reaction between magnesium and an diorganomercury compound [16] (eq (6)). The reaction of dimethylmercury or divinylmercury with magnesium metal proceeds at ca 60 °C, but diphenylmercury requires heating at 150 °C for... 

In further efforts to show the similarities to lithium alkyls, the ylid was treated with diphenylmercury yielding phenyllithium by an exchange reaction 39>. 

Daniel and Paetsch carried out a reaction of the lithium bromide complex of trimethylammoniummethylide with diphenylmercury to clarify the structure of the ylid in solution. Previously Gilman and Jones 49> as well... 

In an attempt to isolate a similar compound by reaction of the ylid with diphenylmercury an amorphous solid was obtained whose infrared spectrum and pyrolysis products were consistent with the expected bis-ylid but which did not give a satisfactory analysis. The zinc adduct was also prepared 176> from fiis-chloromethylzinc and trimethylamine and from the ylid and zinc chloride, but zinc derivatives were not isolated from the reaction of the ylid with dipentyl zinc 110>. 

---