Diphenylmercury

In the IFP- RAM II process, a second catalytic bed constituted of sulfided nickel [124], maintained at a temperature lower than that used for the first one, aUows a complete elimination of metallic mercury (see Section 18.5). Typical commercial results are excellent (see Section 18.5), less than 3ppb of each contaminant in the process effluent as threshold limit for analysis, 1 ppb of each as expectation. 

---

Diphenylmercury [587-85-9] M 354.8, m 125.5-126 . Sublimed, then crystd from nitromethane or ethanol. If phenylmercuric halides are present they can be converted to phenylmercuric hydroxide which, being much more soluble, remains in the alcohol or benzene used for crystn. Thus, crude material (lOg) is dissolved in warm ethanol (ca 150mL) and shaken with moist Ag20 (ca lOg) for 30min, then heated under reflux for 30min and filtered hot. Concentration of the filtrate by evaporation gives diphenylmercury, which is recrystd from benzene [Blair, Bryce-Smith and Pengilly J Chem Soc 3174 7959]. TOXIC. 

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

Diphenylselenium dichloride has been prepared from diphenyl selenide 2,3 by the action of chlorine and by treatment first with nitric acid and then hydrochloric acid. Triphenylselenonium chloride has been prepared by fusing together diphenylmercury... 

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... 

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)... 

Fig. 1 Reflectance scan of a chromatogram track with 30 ng substance (calculated as Hg) per chromatogram zone 1 = methylmercuric chloride, 2 = ethylmercuric chloride, 3 = phenyl-mercuric chloride, 4 = dimethylmercury, 5 = diphenylmercury.

Formation of labeled molecules has been studied in a few cases, but has not been exploited usefully. Various radioactive organomercury compounds have been prepared diphenylmercury (33, 90), fluorescein (53), and chloromeredrin (43). A number of other potentially useful syntheses could doubtless be developed with a wide variety of nuclides with easily detectable y-rays—pharmaceuticals, pesticides, physiological tracers, oil-soluble markers for labeling oil shipments, and so on—if it could be established what molecules are of interest to the various consumers ... 

Despite the extensive history of organozinc chemistry, the first solid-state structure of a Lewis base-free diorganozinc compound with cr-bound ligands, namely diphenylzinc, was not reported until 1990.37 Diphenylzinc was synthesized by the transmetallation of diphenylmercury with metallic zinc (Scheme 10) and, after multiple sublimations, obtained halide free in 67% yield. 

Suitable diphenylmercury is available from Orgmet, Hampstead, New Hampshire, or it can be prepared by the procedxire of Gilman and Brown. ... 

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]. 

Triphenyl sulphur, selenium and telurium cations are reductively cleaved at less negative potentials, moving down the periodic table (Table 5.4). At the first po-larographic wave, a one-electron process results in the formation of phenyl radicals, probably adsorbed on the mercury surface. Only the reaction of triphenylsul-phonium ions has been studied in detail and the products are diphenylsulphide and diphenylmercury. A second polarographic wave has E/, = -1.33 to -1,39 V vs. see over the range of pH 5 to 12 and reduction at the plateau of this wave gives diphenylsulphide and benzene [53]. 

Ladenburg in 1873 synthesized phenyltrichlorosilane, CeHsSiCls by heating silicon tetrachloride with diphenylmercury ... 

By reacting 2.4.6-triphenyl-X -phosphorin with diphenylmercury at high temperatures, Markl was able to induce addition of two carbon groups to the phosphorus (Method D, p. 79). 

Diphenylfuroxane, 399 Diphenylmercury, 401 frans-3,5-Diphenyl-l-pyrazoline, 312 4-(4-Diphenyl)semicarbazide, 195... 

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... 

---