Phosphide-containing

Rather unusually, trialkyl phosphates have been prepared by the oxygenation of mixtures of alcohols and zinc phosphide containing... 

There are many ternary phosphides containing rare earth elanents and a number of these exhibit very varied and interesting magnetic properties. Isostructural series are formed by compounds of types MNi4P2,... 

The inhibition mechanisms described above are only operative in a simation in which Ti is in soUd solution, therefore aU precipitation of phases rich in Ti that occur before irradiation (tempered materials) or during irradiation (carbides, y phases, etc.) could make the previous mechanisms inefficient. Thus, for example, precipitation of TiC and phosphides containing Ti must not be too abimdant to avoid Ti and phosphorus being eliminated from the solid solution. However, if other elements such as Nb can advantageously replace Ti in these phases (Section 8.3.2), an increase in the swelling resistance is expected. Therefore, this is the advantage of the double stabilization that will be discussed below. 

Known scandium phosphides contain 50 or less at.% of phosphorus and in this w they differ in principle from other rare-earth phosphides. The crystal structures of scandium phosphides (except ScP) are characterized by a trigonal-prismatic coordination of phosphorus atoms. They are more closely related to the structures of the IVa transition-metal (Zr and Hf) phosphides than with the other rare-earth phosphides. 

In most cases, the energy of a nonmetal atom is lowered by the addition of an electron. However, energy is always required to add more than one electron. The necessary energy is often supplied by other processes that occur simultaneously (such as an attraction between positive and negative ions). Nonmetal ions with a charge of —3 are rare. However, some metal nitrides containing the nitride ion, and some metal phosphides containing the phosphide ion, P , are known. 

The supplanting of germanium-based semiconductor devices by shicon devices has almost eliminated the use of indium in the related ahoy junction (see Semiconductors). Indium, however, is finding increased use in III—V compound semiconductors such as indium phosphide [22398-80-7] for laser diodes used in fiber optic communication systems (see Electronic materials Fiber optics Light generation). Other important indium-containing semiconductors include indium arsenide [1303-11-3] indium antimonide [1312-41 -0] and copper—indium—diselenide [12018-95-0]. 

The extremely toxic and flammable gas phosphine is safely and conveniently generated for the fumigation of grain in sacks or bins from 3-g tablets containing aluminum phosphide and ammonium carbamate which produce 1 g of phosphine in the presence of moisture. 

Phosphides. Compounds of phosphoms containing the more electropositive elements are generally called phosphides. A large number of binary phosphides as well as many ternary mixed-metal phosphides, metal phosphide nitrides, etc, are known. Some binary phosphides, such as those of nickel, exhibit a variety of stoichiometries (Ni P, Ni P2, Nq2P5, Ni2P, Ni P, NiP, NiP2, NiP ), whereas others, such as aluminum, form only one (AlP). Metalloids such as B and Si also form phosphides. 

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. 

The alkah metal phosphides of formula M P and the alkaline-earth phosphides of formula M2P2 contain the P anion. Calcium diphosphide [81103-86-8] CaP2, contains P reaction with water Hberates diphosphine and maintains the P—P linkage. 

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). 

Phosphides are binary compounds containing anionic phosphorus (P ). Heavy metal, alkali, and alkaline earth metal phosphides exist but few of them are commercially important. Phosphides hydrolyze to the flammable and toxic gas phosphine (PH3). The hydrolysis reaction of aluminum phosphide is given below ... 

In addition to the heteronuclear clusters considered in the preceding paragraphs. As, Sb and Bi also form homonuclear clusters. We have already seen that alkaline earth phosphides M3P14 contain the [Pv] cluster isoelectronic and isostructural with P4S3, and the analogous clusters [Asy] " and [Sbv] have also been synthesized. Thus, when As was heated with metallic Ba at 800° C, black lustrous prisms of BasAs were obtained, isotypic with Ba3Pi4 these contained the [Asv] anion with dimensions as shown in Fig. 13.25(a).Again,... 

Fig. 3.38 Typical graphitic residue, containing graphite flakes and some unattacked phosphide eutectic...

Phosphorus appears to have a beneficial effect on the growth rate. At sub-critical temperatures it helps to stabilise the carbide, while at temperatures up to about 900°C the presence of the hard phosphide eutectic network restricts the deformation to which the much more ductile matrix would otherwise be subject. Since the phosphide eutectic melts at about 950°C, irons containing appreciable amounts of this constituent should clearly not be exposed to this temperature. 

Ferrosilicon containing 30-75% of silicon is hazardous, particularly when finely divided, and must be kept in a moisture-tight drum. In contact with water, the impurities present (arsenide, carbide, phosphide) evolve extremely poisonous arsine, combustible acetylene and spontaneously flammable phosphine [1 2],... 

Pasek and Lauretta (University of Arizona, Tucson) point to a further important source of phosphate they studied the corrosion of phosphide minerals from iron meteorites under various conditions in aqueous solution, e.g., using NaHCCb as a buffer, or in solutions containing MgCh and CaCL, as well as in the presence of ethanol and acetic acid. 

The reaction of Ba[P(SiMe3)2]2(THF)2 with diphenylbutadiyne in toluene for 12 days induces a m-addition of the diyne to the phosphide, followed by a 1,3-silyl group shift and ring closure. The dinuclear complex 132 is then isolated in good yield.283 Its complex structure contains Ba-C a bonds (2.881(5), 2.899(5) A), side-on Ba-alkyne (3.003(6), 3.363(6) A) and arene interactions, and Ba-phospholide bonds (Ba-P = 3.487(2) A) (Figure 65). 

Fig. 18 Normalized intensity of plasmon loss peak in the Co 2p3/2 spectrum vs. difference in electronegativity for Co-containing phosphides. The dashed line indicates the value for Co metal. Reprinted with permission from [60], Copyright Elsevier...

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