Phosphide

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A portion of the structure of Page Module:Chem2/styles.css has no content.Cu3P, highlighting the highly crosslinked nature common to many transition metal phosphides (Cu = orange, P = purple).

In chemistry, a phosphide is a compound containing the Page Module:Chem2/styles.css has no content.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.

Binary phosphides

Binary phosphides include phosphorus and one other element. An example of a group 1 phosphide is sodium phosphide (Page Module:Chem2/styles.css has no content.Na3P). Other notable examples include aluminium phosphide (Page Module:Chem2/styles.css has no content.AlP) and calcium phosphide (Page Module:Chem2/styles.css has no content.Ca3P2), which are used as pesticides, exploiting their tendency to release toxic phosphine upon hydrolysis. Magnesium phosphide (Page Module:Chem2/styles.css has no content.Mg3P2) also is moisture sensitive. Indium phosphide (Page Module:Chem2/styles.css has no content.InP) and gallium phosphide (Page Module:Chem2/styles.css has no content.GaP) are used as a semi-conductors, often in combination of related arsenides.[3] Copper phosphide (Page Module:Chem2/styles.css has no content.Cu3P) 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:

Page Module:Chem2/styles.css has no content.Ca3P2 + 6 H2O → 3 Ca(OH)2 + 2 PH3
Coordination environment around Cu in Page Module:Chem2/styles.css has no content.Cu3P. Two pairs of Cu atoms are eclipsed.

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 Page Module:Chem2/styles.css has no content.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: Page Module:Chem2/styles.css has no content.K3P, Page Module:Chem2/styles.css has no content.K4P3, Page Module:Chem2/styles.css has no content.K5P4, Page Module:Chem2/styles.css has no content.KP, Page Module:Chem2/styles.css has no content.K4P6, Page Module:Chem2/styles.css has no content.K3P7, Page Module:Chem2/styles.css has no content.K3P11, Page Module:Chem2/styles.css has no content.KP10.3, Page Module:Chem2/styles.css has no content.KP15. Eight mono- and polyphosphides of nickel also exist: (Page Module:Chem2/styles.css has no content.Ni3P, Page Module:Chem2/styles.css has no content.Ni5P2, Page Module:Chem2/styles.css has no content.Ni12P5, Page Module:Chem2/styles.css has no content.Ni2P, Page Module:Chem2/styles.css has no content.Ni5P4, Page Module:Chem2/styles.css has no content.NiP, Page Module:Chem2/styles.css has no content.NiP2, Page Module:Chem2/styles.css has no content.NiP3).[2]

Two polyphosphide ions, P4−
3 found in K
4P
3 and P5−
4 found in Page Module:Chem2/styles.css has no content.K5P4, 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, Page Module:Chem2/styles.css has no content.Ni2P and Page Module:Chem2/styles.css has no content.Ni12P5. These compounds were synthesized through a solid-liquid reaction between Page Module:Chem2/styles.css has no content.NiCl2·12H2O 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 Page Module:Chem2/styles.css has no content.K2P16 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 Page Module:Chem2/styles.css has no content.P≡Mo(NR2)3, 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 Page Module:Chem2/styles.css has no content.R2PM where R is an organic substituent and M is a metal. One example is lithium diphenylphosphide.

Natural examples

The mineral schreibersite Page Module:Chem2/styles.css has no content.(Fe,Ni)3P is common in some meteorites.

References

Page Template:Reflist/styles.css has no content.

  1. ^ Page Module:Citation/CS1/styles.css has no content.Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
  2. ^ 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
  3. ^ Page Module:Citation/CS1/styles.css has no content.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" (PDF). Journal of Materials Chemistry. 13 (8): 1930. doi:10.1039/b304084b.
  4. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ Page Module:Citation/CS1/styles.css has no content.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. Retrieved 28 March 2024.
  6. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ Page Module:Citation/CS1/styles.css has no content.von Schnering, Hans-Georg; Hönle, Wolfgang (1988). "Bridging Chasms with Phosphides". Chemical Reviews. 88: 243–273. doi:10.1021/cr00083a012.
  9. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ Page Module:Citation/CS1/styles.css has no content.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. ^ Page Module:Citation/CS1/styles.css has no content.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. CiteSeerX 10.1.1.666.8019. doi:10.1021/cr9003709. PMID 20175534.

Template:Phosphides Template:Monatomic anion compounds

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