Group phosphides

Methods of Preparation—Alkali Phosphides—Alkaline Earth Phosphides— Copper, Silver and Gold Phosphides—Zino Group Phosphides—Boron and Aluminium Phosphides—Titanium Group Phosphides—Tin and Lead Phosphides—Arsenic, Antimony and Bismuth Phosphides—Chromium, Molybdenum and Tungsten Phosphides—Manganese Phosphides—Iron, Cobalt and Niokel Phosphides—Platinum Phosphides. 

As shown in Reactions (26)-(28), similar routes can be used to prepare iron group phosphides. 

This group is exemplified by nitrides, carbides, and phosphides. Nitrides will react with water to generate ammonia (NH3), which can be released depending on how alkaline the solution becomes. It is unlikely that sufficient NH3 will be produced under normal circumstances to create a hazard. 

Few industrial uses have so far been found for phosphides. Ferrophosphorus is produced on a large scale as a byproduct of P4 manufacture, and its uses have been noted (p. 480). Phosphorus is also much used as an alloying element in iron and steel, and for improving the workability of Cu. Group 3 monophosphides are valuable semiconductors (p. 255) and Ca3P2 is an important ingredient in some navy sea-flares since its reaction with water releases spontaneously flammable... 

Compounds with Sc, Y, lanthanoids and actinoids are of three types. Those with composition ME have the (6-coordinated) NaCl structure, whereas M3E4 (and sometimes M4E3) adopt the body-centred thorium phosphide structure (Th3P4) with 8-coordinated M, and ME2 are like ThAsi in which each Th has 9 As neighbours. Most of these compounds are metallic and those of uranium are magnetically ordered. Full details of the structures and properties of the several hundred other transition metal-Group 15 element compounds fall outside the scope of this treatment, but three particularly important structure types should be mentioned because of their widespread occurrence and relation to other structure types, namely C0AS3,... 

The reaction of the hydrides of both the Groups nib and Vb elements is also used notably in the production of boron phosphide at 950-1000°C as follows ... 

A further interesting feature of the gallium phosphides and arsenides is that the former compounds are colorless whereas the latter range from yellow to orange. Color can arise from ir- ir transitions in main group compounds for example, in the disilylenes and digermenes R2E = ER2 (E = Si, Ge) in which the it- tt transitions occur at lower energy than... 

Phosphido-bridged multinuclear complexes have been formed from zinc chloride of the form [Zn4(PPh2)4Cl4(PRR 2)2], where R and R are alkyl or phenyl groups. Related tetrameric structures can be formed with a bridging dialkyl phosphide or (trimethyl)silylphenyl phosphide.303... 

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). 

Most nonmetallic elements will react with the group IA and IIA metals to give binary compounds. Heating the metals with nitrogen or phosphorus gives nitrides and phosphides of the metals. 

As the solid state structures of heterocyclic group 13 amides, phosphides and arsenides have been reviewed in the past,76 they will not be discussed here. Instead, the solid state structures of group 13 stibides and bismuthides will be described in detail. 

In the last decade, numerous compounds of these types have been the subject of detailed CVD studies, demonstrating their potential for the deposition of the corresponding binary materials. Most of the work has concentrated on binary nitrides and phosphides, while the deposition of binary MSb films has been studied to a far lesser extent. The lack of potential precursors has been the major problem for the deposition of group 13-antimonide films for many years. Only a very few group 13-Sb compounds have been known until we and Wells established general synthetic pathways as was shown in Sections 2 and 3. Consequently, detailed investigations concerning their potential to serve for the deposition of the desired materials... 

The alkoxide group R is chosen so that the heavier alkali metal alkoxide MOR is soluble in ether or hydrocarbon solvents and so the by-product LiOR may easily be separated from the desired heavier alkali metal phosphide/arsenide (which is often insoluble in weakly or noncoordinating solvents such as ethers and hydrocarbons). 

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