Phosphide

In chemistry, a phosphide is a compound containing the P3− 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.

## Contents

* 1 Binary phosphides
* 2 Polyphosphides
* 3 Preparation of phosphide and polyphosphide materials
* 4 Molecular phosphides
* 5 Organic phosphides
* 6 Natural examples
* 7 References

## Binary phosphides

Binary phosphides include phosphorus and one other element. An example of a group 1 phosphide is sodium phosphide (Na
3P). Other notable examples include aluminium phosphide (AlP) and calcium phosphide (Ca

2), which are used as pesticides, exploiting their tendency to release toxic phosphine upon hydrolysis. Magnesium phosphide (Mg

2) also is moisture sensitive. Indium phosphide (InP) and gallium phosphide (GaP) are used as a semi-conductors, often in combination of related arsenides.[3] Copper phosphide (Cu
3P) 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:

2 \+ 6 H
2O → 3 Ca(OH)
2 \+ 2 PH

File:Improved CuCoordSphereCu3P.tif

## Polyphosphides

Structure of the P3−7 subunit as found in M3P7 (M = alkali metal). Close up on the structure of SnP3, highlighting the bonding around P (violet) and Sn (gray).

Polyphosphides contain P–P bonds. The simplest polyphosphides would be derivatives of P4−2. The free anions are rarely encountered because they are so basic. Most members follow the octet rule.

Well studied polyphosphides are derivatives of P3−7.[4] This Zintl cluster anion is obtained with diverse alkali metal derivatives.

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-P6−6 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 P3−11 ions and polymeric chain anions (e.g. the helical (P−)n ion) and complex sheet or 3-D anions.[7] The range of structures is extensive. Potassium has nine phosphides: K
3P, K

3, K

4, KP, K

6, K

7, K

11, KP
10.3, KP
15. Eight mono- and polyphosphides of nickel also exist: (Ni
3P, Ni

2, Ni
12P
5, Ni
2P, Ni

4, NiP, NiP
2, NiP
3).[2]

Two polyphosphide ions, P4−3 found in K4P3 and P5−4 found in K

4, 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, Ni
2P and Ni
12P
5. These compounds were synthesized through a solid-liquid reaction between NiCl
2 * 12H2O 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.

Structure of terminal phosphido complexes of Mo.

A method for the preparation of K

16 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 P≡Mo(NR

3, where R is a bulky organic substituent.[11]

## Organic phosphides

See also: Chemistry:Organophosphine and Phosphaalkyne

Many organophosphides are known. Common examples have the formula R
2PM where R is an organic substituent and M is a metal. One example is lithium diphenylphosphide.

## Natural examples

The mineral schreibersite (Fe,Ni)
3P is common in some meteorites.

## References

1. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
2. ↑ 2.0 2.1 2.2 Von Schnering, H.G. and Hönle , W. (1994) "Phosphides - Solid-state Chemistry" in Encyclopedia of Inorganic Chemistry. R. Bruce King (ed.). John Wiley & Sons ISBN 0-471-93620-0
3. ↑ Blackman, C. S.; Carmalt, C. J.; O'Neill, S. A.; Parkin, I. P.; Molloy, K. C.; Apostolico, L. (2003). "Chemical vapour deposition of group Vb metal phosphide thin films". Journal of Materials Chemistry 13 (8): 1930. doi:10.1039/b304084b. http://discovery.ucl.ac.uk/143120/1/Blackman_Group_VB_2_Corrected.pdf.
4. ↑ Meyer, Teodoro; Hönle, Wolfgang; von Schnering, Hans Georg (1987). "Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 44. Tricäsiumheptaphosphid Cs3P7: Darstellung, Struktur und Eigenschaften". Zeitschrift für Anorganische und Allgemeine Chemie 552 (9): 69–80. doi:10.1002/zaac.19875520907.
5. ↑ Gullman, Jan; Olofsson, Olle (1 November 1972). "The crystal structure of SnP3 and a note on the crystal structure of GeP3". Journal of Solid State Chemistry 5 (3): 441–445. doi:10.1016/0022-4596(72)90091-6. ISSN 0022-4596. https://www.sciencedirect.com/science/article/abs/pii/0022459672900916. Retrieved 28 March 2024.
6. ↑ Olofsson, Olle; Gullman, Jan; Søtofte, Inger; Beronius, P.; Engebretsen, Jan E.; Ehrenberg, L. (1971). "The Crystal Structure of TlP5". Acta Chemica Scandinavica 25: 1327–1337. doi:10.3891/acta.chem.scand.25-1327.
7. ↑ Jeitschko, W.; Möller, M. H. (1987). "Phosphides and Polyphosphides of the Transition Metals". Phosphorus and Sulfur and the Related Elements 30 (1–2): 413–416. doi:10.1080/03086648708080608.
8. ↑ von Schnering, Hans-Georg; Hönle, Wolfgang (1988). "Bridging Chasms with Phosphides". Chemical Reviews 88: 243–273. doi:10.1021/cr00083a012.
9. ↑ Liu, Zongyi; Huang, Xiang; Zhu, Zhibin; Dai, Jinhui (2010). "A simple mild hydrothermal route for the synthesis of nickel phosphide powders". Ceramics International 36 (3): 1155–1158. doi:10.1016/j.ceramint.2009.12.015.
10. ↑ Dragulescu-Andrasi, Alina; Miller, L. Zane; Chen, Banghao; McQuade, D. Tyler; Shatruk, Michael (March 14, 2016). "Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide". Angewandte Chemie International Edition 55 (12): 3904–3908. doi:10.1002/anie.201511186. PMID 26928980.
11. ↑ Cossairt, B. M.; Piro, N. A.; Cummins, C. C. (2010). "Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus". Chemical Reviews 110 (7): 4164–77. doi:10.1021/cr9003709. PMID 20175534.

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Phosphides

| PH3 |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  |  | He

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Li3P | Be |  |  |  |  |  |  |  |  |  |  | BP | CP | N | O | F | Ne
Na3P | Mg |  |  |  |  |  |  |  |  |  |  | AlP | Si | P | S | Cl | Ar
K3P | Ca3P2
CaP | ScP | TiP | V | CrP
Cr3P | Mn | Fe2P | CoP
Co2P
Co3P2 | NixPy | Cu3P | Zn3P2 | GaP | Ge | As | Se | Br | Kr
Rb | Sr | YP | ZrP
ZrP2 | Nb | MoP
MoP2 | Tc | Ru2P | Rh | Pd | Ag3P | Cd | InP
GaInP2 | Sn | SbP | Te | I | Xe
Cs3P | Ba | *  | Hf | Ta | W | Re | OsP2 | Ir | Pt | Au | Hg | Tl | PbP7 | BiP | Po | At | Rn
Fr | Ra | **  | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og
|  | ↓ |  |  |  |  |  |  |  |  |  |  |  |  |  |  |
| * | LaP | CeP | Pr | Nd | Pm | Sm | EuP | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu |
| ** | AcP | Th | Pa | UP | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr |

Template:Monatomic anion compounds

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