Phosphines mercury compounds

RM can be a traditional Grignard reagent or an organolithium, 2inc, aluminum, or mercury compound. The Grignard route is employed commercially for production of tertiary phosphines, even though these reactions are subject to side reactions. Yields are often low, eg, 40—50% for (C4H )2P prepared via a Grignard reaction (18). A phosphoms—carbon bond can form from the metathetical reaction of a phosphoms haUde and a pseudohaUde salt. 

Mercury and mercury compounds Nickel and nickel compounds Phosphine (= hydrogen phosphide)... 

Bases such as amines, phosphines, or phosphites were found to react with the heterometal catalysts in three different ways Coordination to the heterometal without CO displacement, substitution of CO, and disproportionation, respectively. The latter reaction occurred only with the mercury compound, which reacted with amines and phosphines... 

The mercury compound Hg[Co(CO)4]2 appears to be the most stable of these metal cobalt tetracarbonyl derivatives, especially with respect to air oxidation. It reacts with the phosphines R3P (R = phenyl, cyclohexyl, or ethyl) at room temperature to form the yellow, sparingly soluble solids Hg[Co(CO)3PR3]2 26). The phenyl derivative may also be obtained from Na[Co(CO)3P(C6Hs)3] and an appropriate mercury derivative. Treatment of Hg[Co(CO)4]2 with pyridine liberates free mercury to form the salt [Co(py)d[Co(CO)4]2(26)... 

Mercury(II) nitrate Acetylene, aromatics, ethanol, hypophosphoric acid, phosphine, unsaturated organic compounds... 

Mass effects due to some ions in salts. It is generally observed that there is a greater instability amongst compounds containing heavy atoms compared with elements in the first periods of the periodic tabie.This can be observed by analysing enthalpies of formation of ammonia, phosphine, arsine and stibine (see previous table for the last three). In the same way, it is easier to handle sodium azide than lead azide, which is a primary explosive for detonators. It is exactly the same with the relatively highly stable zinc and cadmium thiocyanates and the much less stable mercury thiocyanate. 

Mercury(II) cyanide Mercury(I) nitrate Mercury(II) nitrate Fluorine, hydrogen cyanide, magnesium, sodium nitrite Phosphorus Acetylene, aromatics, ethanol, hypophosphoric acid, phosphine, unsaturated organic compounds... 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

Photolysis of carbethoxymethylenetriphenylphosphine in cyclohexene yields benzene, ethyl acetate, ethyl cyclohexylacetate, ethyl cyclohex-2-ene-l-acetate, phenylcyclohexane l,T-bicyclohex-2-ene (Quantum yield measured by use of a low pressure mercury lamp as a light source no yield in material) and diphenyl phosphinic acid. In this case, no triphenylphosphine is produced. On the other hand, pyrolysis of this carbethoxymethy-lene compound shows that only P=C bond fission occurs91. Using acetylmethylene-triphenylphosphine, the observed products are analogous20. However, the irradiation of... 

Three phosphine adducts are known for the mercury xanthates and each structure reveals that the aggregation observed in the parent compounds no longer persists. 

In contrast to the tertiary amines, trialkylphosphines have strong donor properties and form exceedingly stable coordination complexes with a wide variety of metal salts such as those of univalent copper and gold, and bivalent platinum, palladium, and mercury.1 Like phosphine itself, many of these tertiary alkylphosphines are highly flammable, toxic, and extremely susceptible to air oxidation. Ease of oxidation first decreases and then increases as the alkyl group becomes larger.2 3,4 5 The n-butyl compound is thus a convenient member of this group for preparation. 

Samaan used reduction at a mercury cathode to convert the phosphonium salt 33 to the phosphine (34) (79PS89). This gave the opposite stereoisomer from that available as the major product (35) from base hydrolysis followed by silane reduction. The stereochemistry of each compound was established by NMR analysis. 

Many studies on the direct reaction of methyl chloride with silicon-copper contact mass and other metal promoters added to the silicon-copper contact mass have focused on the reaction mechanisms.7,8 The reaction rate and the selectivity for dimethyldichlorosilane in this direct synthesis are influenced by metal additives, known as promoters, in low concentration. Aluminum, antimony, arsenic, bismuth, mercury, phosphorus, phosphine compounds34 and their metal complexes,35,36 Zinc,37 39 tin38-40 etc. are known to have beneficial effects as promoters for dimethyldichlorosilane formation.7,8 Promoters are not themselves good catalysts for the direct reaction at temperatures < 350 °C,6,8 but require the presence of copper to be effective. When zinc metal or zinc compounds (0.03-0.75 wt%) were added to silicon-copper contact mass, the reaction rate was potentiated and the selectivity of dimethyldichlorosilane was enhanced further.34 These materials are described as structural promoters because they alter the surface enrichment of silicon, increase the electron density of the surface of the catalyst modify the crystal structure of the copper-silicon solid phase, and affect the absorption of methyl chloride on the catalyst surface and the activation energy for the formation of dimethyldichlorosilane.38,39 Cadmium is also a structural promoter for this reaction, but cadmium presents serious toxicity problems in industrial use on a large scale.41,42 Other metals such as arsenic, mercury, etc. are also restricted because of such toxicity problems. In the direct reaction of methyl chloride, tin in... 

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