Phosphide
In chemistry, a phosphide is a compound containing the Template:Chem2 ion or its equivalent. Many different phosphides are known, with widely differing structures.[1] Most commonly encountered on the binary phosphides, i.e. those materials consisting only of phosphorus and a less electronegative element. Numerous are polyphosphides, which are solids consisting of anionic chains or clusters of phosphorus. Phosphides are known with the majority of less electronegative elements with the exception of Hg, Pb, Sb, Bi, Te, and Po.[2] Finally, some phosphides are molecular.
Binary phosphides
Binary phosphides include phosphorus and one other element. An example of a group 1 phosphide is sodium phosphide (Template:Chem2). Other notable examples include aluminium phosphide (Template:Chem2) and calcium phosphide (Template:Chem2), which are used as pesticides, exploiting their tendency to release toxic phosphine upon hydrolysis. Magnesium phosphide (Template:Chem2) also is moisture sensitive. Indium phosphide (Template:Chem2) and gallium phosphide (Template:Chem2) are used as a semi-conductors, often in combination of related arsenides.[3] Copper phosphide (Template:Chem2) illustrates a rare stoichiometry for a phosphide. These species are insoluble in all solvents - they are 3-dimensional solid state polymers. For those with electropositive metals, the materials hydrolyze:
Polyphosphides
Polyphosphides contain Template:Chem2 bonds. The simplest polyphosphides would be derivatives of Template:Chem. The free anions are rarely encountered because they are so basic. Most members follow the octet rule.
Well studied polyphosphides are derivatives of Template:Chem.[4]
The nomenclature for polyphosphides can be deceptive. As confirmed by X-ray crystallography tin triphosphide and germanium triphosphide are not triphosphides, but hexaphosphides. They consist of ruffled cyclo-Template:Chem subunits.[5] Another example of deceptive nomenclature is "thorium pentaphosphide", which consists of a polymeric polyphosphide related to Hittorf's phosphorus.[6]
Several polyphosphides contain the cluster Template:Chem ions and polymeric chain anions (e.g. the helical Template:Chem ion) and complex sheet or 3-D anions.[7] The range of structures is extensive. Potassium has nine phosphides: Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2. Eight mono- and polyphosphides of nickel also exist: (Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2, Template:Chem2).[2]
Two polyphosphide ions, Template:Chem found in Template:Chem and Template:Chem found in Template:Chem2, are radical anions with an odd number of valence electrons.[2]
Preparation of phosphide and polyphosphide materials
There are many ways to prepare phosphide compounds. One common way involves heating a metal and red phosphorus (P) under inert atmospheric conditions or vacuum. In principle, all metal phosphides and polyphosphides can be synthesized from elemental phosphorus and the respective metal element in stoichiometric forms. However, the synthesis is complicated due to several problems. The exothermic reactions are often explosive due to local overheating. Oxidized metals, or even just an oxidized layer on the exterior of the metal, causes extreme and unacceptably high temperatures for beginning phosphorination.[8] Hydrothermal reactions to generate nickel phosphides have produced pure and well crystallized nickel phosphide compounds, Template:Chem2 and Template:Chem2. These compounds were synthesized through a solid-liquid reaction between Template:Chem2 and red phosphorus at 200 °C for 24 and 48 hours, respectively.[9]
Metal phosphides are also produced by reaction of tris(trimethylsilyl)phosphine with metal halides. In this method, the halide is liberated as the volatile trimethylsilyl chloride.
A method for the preparation of Template:Chem2 from red phosphorus and potassium ethoxide has been reported.[10]
Molecular phosphides
Compounds with triple bonds between a metal and phosphorus are rare. The main examples have the formula Template:Chem2, where R is a bulky organic substituent.[11]
Organic phosphides
Script error: No such module "Labelled list hatnote". Many organophosphides are known. Common examples have the formula Template:Chem2 where R is an organic substituent and M is a metal. One example is lithium diphenylphosphide. The Zintl cluster Template:Chem is obtained with diverse alkali metal derivatives.
Natural examples
The mineral schreibersite Template:Chem2 is common in some meteorites.
References
Template:Reflist Template:Phosphides Template:Monatomic anion compounds
- ↑ Template:Greenwood&Earnshaw
- ↑ a b c Von Schnering, H.G. and Hönle , W. (1994) "Phosphides - Solid-state Chemistry" in Encyclopedia of Inorganic Chemistry. R. Bruce King (ed.). John Wiley & Sons Template:ISBN
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