Phosphide preparation

Aguilar, A.M. and Daigle, D., Vinyl halide displacement by metallo organo-phosphides. Preparation of fra s-(f-styryldiphenylphosphine oxide and sulfide, /. Org. Chem., 30, 2826, 1965. 

Our experience has shown that the hydrolysis of aluminium phosphide with cold water is the most suitable method for the laboratory preparation of phosphine. Here it is important that the aluminium phosphide be as pure as possible in order to avoid the formation of spontaneously inflammable phosphine. The presence of small quantities of diphosphine and also higher phosphines are responsible for this spontaneous inflammability 96.276-278) jj. gp, pears, however, that these are only formed when P—P bonds are already present in the phosphide. Accordingly the hydrolysis of aluminium phosphide, prepared from the elements with phosphorus in slight excess, always leads to spontaneously inflammable phosphine. The formation of diphosphine and higher phosphines from aluminium or alkaline earth metal phosphides, which contain excess phosphorus, can be easily understood when the lattices of these compounds are considered. 

Zeolite mordenite Size-quantized indium phosphide prepared in zeolite cages... 

B. Pelletier23 obtained an antimony phosphide by the action of molten antimony on metaphosphoric acid with or without admixed carbon. B. Pelletier, and G. Landgrebe obtained a phosphide by the action of phosphorus on molten antimony, although W. Ramsay and R. W. E. Mclvor could obtain a product with only 1546 per cent, by direct action. The last-named prepared antimony monophosphide, SbP, by the action of phosphorus on a soln. of antimony tribromide in carbon disulphide. M. Ragg could not prepare the monophosphide by this process, nor by the action of phosphine on tartar emetic, or antimony trichloride. The phosphide prepared by the fusion processes is a brittle, white mass with a crystalline fracture the precipitated product is a red powder insoluble in carbon disulphide, ether, and benzene. O. Ruff found that phosphorus reacts with antimony chloride in the presence of aluminium chloride—vide supra, arsenic oxyphosphide. 

Alkaline Earth Phosphides.—An impure calcium phosphide, made by exposing lime at a red heat to the vapour of phosphorus, was used in the preparation of phosphine.2 Calcium phosphide probably is also formed during the manufacture of phosphorus by the electric furnace method g.v.). It has been prepared by heating calcium phosphate and lamp black in the electric arc furnace, and appeared as a crystalline reddish-black substance.3 Calcium phosphide prepared in this manner is only acted upon slowly by water at the ordinary temperature, but readily by aqueous solutions of strong acids. Concentrated nitric and sulphuric acids, and oxygen and chlorine, do not attack it at ordinary temperatures, but on heating it is oxidised, e.g. by chlorine above 100° C. and by oxygen above 300° C. 

Solid Hydrogen Phosphide —Preparation, Properties, Chemical Reactions. 

Phosphides.—An arc melting technique, which offers advantages in purity of product and higher attainable temperatures over the conventional approach to phosphide preparation, has been used to re-examine the V-P system (the V-As and Cr-As systems were also investigated). The phases in the V-P system were confirmed, but in the corresponding arsenic system two new orthorhombic phases have been identified. 

B.--I Exposure. Anticoagulant rodenticides with and-vitamin K activity, diolecalcifenil (vitamin D3)-based rodenticides, and zinc or ahaninuro phosphide preparations are... 

Indium also combines with nonmetaUic elements and with metalloids such as N, P, Sb, As, Te, and Se. Many of the latter compounds ate semiconducting as ate the oxide and sulfide. Indium antimonide [1312-41 -0], InSb indium arsenide [1303-11-3], In As and indium phosphide [22398-80-7], InP, ate the principal semiconducting compounds. These ate all prepared by direct combination of the highly purified elements at elevated temperature under controlled conditions. 

Semiconductors. Phosphine is commonly used in the electronics industry as an -type dopant for siUcon semiconductors (6), and to a lesser extent for the preparation of gaUium—indium—phosphide devices (7). For these end uses, high purity, electronic-grade phosphine is required normally >99.999% pure. The main impurities that occur in phosphine manufactured by the acid process are nitrogen [7727-37-9] hydrogen [1333-74-0] arsine [7784-42-17, carbon dioxide [124-38-9], oxygen [7782-44-7], methane [74-82-8], carbon monoxide [630-08-0], and water [7732-42-1]. Phosphine is purified by distillation under pressure to reduce the level of these compounds to <1 ppm by volume. The final product is sold as CYPURE (Cytec Canada Inc.) phosphine. 

Some phosphides, such as titanium phosphide [12037-65-9] TiP, can be prepared bypassing phosphine over the metal or its haUde. Reaction of phosphine with heavy metal salt solutions often yields phosphines that may contain unsubstituted hydrogens. Phosphides may also be prepared by reducing phosphoms-containing salts with hydrogen, carbon, etc, at high temperatures, the main example of which is the by-product formation of ferrophosphoms in the electric furnace process for elemental phosphoms. Phosphoms-rich phosphides such as vanadium diphosphide [12037-77-3] may be converted to lower phosphides, eg, vanadium phosphide [12066-53-4] by thermal treatment. 

Copper and tin phosphides are used as deoxidants in the production of the respective metals, to increase the tensile strength and corrosion resistance in phosphor bronze [12767-50-9] and as components of brazing solders (see Solders and brazing alloys). Phosphor bronze is an alloy of copper and 1.25—11 wt % tin. As tin may be completely oxidized in a copper alloy in the form of stannic oxide, 0.03—0.35 wt % phosphoms is added to deoxidize the alloy. Phosphor copper [12643-19-5] is prepared by the addition of phosphoms to molten copper. Phosphor tin [66579-64-4] 2.5—3 wt % P, is made for the deoxidation of bronzes and German silver. 

The phosphido complex, Th(PPP)4 [143329-04-0], where PPP = P(CH2CH2P(CH2)2)2) has been prepared and fully characterized (35) and represents the first actinide complex containing exclusively metal—phosphoms bonds. The x-ray stmctural analysis indicated 3-3-electron donor phosphides and 1-1-electron phosphide, suggesting that the complex is formally 22-electron. Similar to the amido system, this phosphido compound is also reactive toward insertion reactions, especially with CO, which undergoes a double insertion (35,36). 

Titanium Phosphides. The titanium phosphides (154) include Ti P [12037-66-0], Ti P, and TiP (163). Titanium monophosphide [12037-65-9] TiP, can be prepared by beating phosphine with titanium tetrachloride or titanium sponge. Alternatively, titanium metal may be heated with phosphoms ia a sealed tube. The gray metallic TiP is slightly phosphoms-deficient (TiPQ has a density of 408(0) kg/m, and displays considerable... 

The phosphides tricadrnium diphosphide [12014-28-7], Cd2P2, cadmium diphosphide [12133-44-7], CdP2, and cadmium tetraphosphide [12050-26-9], CdP, may all be prepared by indirect fusion of the elements, usually by passing phosphoms vapors, in a nitrogen or hydrogen carrier gas. 

The most general preparative route to phosphides (Faraday s method) is to heat the metal with the appropriate amount of red P at high temperature in an inert atmosphere or an evacuated sealed tube ... 

Most of these compounds were originally prepared by liquid-phase epitaxy. That process is now largely replaced by MOCVD, particularly in the case of gallium arsenide, gallium arsenic phosphide, and gallium aluminum phosphide. 

Reactions of alkyl halides with alkaU metal phosphides [39-41], addition reactions of olefins with PHj [42] or the pyrolytic cleavage of P-0 bonds in RPO2H2 [43] are also reported for the preparation of alkyl/aryl functionalized primary... 

In the most versatile preparation of phosphaalkynes, acid chlorides such as pivaloyl chloride [27] are reacted either with P(SiMe3)3 1692, with formation of TCS 14, or with (Me3Si)2PLi 1725 [26] to give the phosphides 1726 [28, 29], which eliminate hexamethyldisiloxane (HMDSO) 7 in the presence of catalytic amounts of NaOH [28] either in a solvent or more efficiently without a solvent at 120-200 °C [29, 30] to afford, via 1727, the corresponding phosphaalkynes 1728 and HMDSO 7 [1, 4] (Scheme 11.7). 

Preparation of Phosphines from Metallated Phosphines.- It has been shown that phosphide anions may be generated from primary and secondary phosphines under aqueous conditions using concentrated aqueous alkali in DMSO or other dipolar aprotic solvents. 

T. Lundstrom, Preparation and crystal chemistry of some refractory borides and phosphides. Ark. Kemi 31 (1969) 227. 

Phosphides and amides are closely related, as a synthetic route is based on metathesis of metal amides, especially the respective trimethylsilyl amides, with the appropriate free acidic phosphine or an anion derived therefrom. Reaction of metal halides and trisilylphosphines is an alternative for preparing metal phosphides. 

Iseler, G. W. et al., Int. Conf. Indium Phosphide Relat. Mater., 1992, 266 Reaction of beryllium, copper, manganese, thorium or zirconium is incandescent when heated with phosphorus [1] and that of cerium, lanthanum, neodymium and praseodymium is violent above 400°C [2], Osmium incandesces in phosphorus vapour, and platinum bums vividly below red-heat [3], Red phosphorus shows very variable vapour pressure between batches (not surprising, it is an indeterminate material). This leads to explosions when preparing indium phosphide by reactions involving fusion with phosphorus in a sealed tube [4],... 

Contact of one drop of water with a zinc phosphide rodenticide preparation caused ignition. 

---