Phosphide

Binary phosphides include phosphorus and one other element. An example of a group 1 phosphide is sodium phosphide ({{chem2|Na3P}}). Other notable examples include aluminium phosphide ({{chem2|AlP}}) and calcium phosphide ({{chem2|Ca3P2}}), which are used as pesticides, exploiting their tendency to release toxic phosphine upon hydrolysis. Magnesium phosphide ({{chem2|Mg3P2}}) also is moisture sensitive. Indium phosphide ({{chem2|InP}}) and gallium phosphide ({{chem2|GaP}}) are used as a semi-conductors, often in combination of related arsenides.{{Cite journal|last1=Blackman|first1=C. S.|last2=Carmalt|first2=C. J.|author-link2=Claire J. Carmalt|last3=O'Neill|first3=S. A.|last4=Parkin|first4=I. P.|last5=Molloy|first5=K. C.|last6=Apostolico|first6=L.|year=2003|title=Chemical vapour deposition of group Vb metal phosphide thin films|url=http://discovery.ucl.ac.uk/143120/1/Blackman_Group_VB_2_Corrected.pdf|journal=Journal of Materials Chemistry|volume=13|issue=8|pages=1930|doi=10.1039/b304084b}} Copper phosphide ({{chem2|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:

:{{chem2|Ca3P2 + 6 H2O → 3 Ca(OH)2 + 2 PH3}}

File:Improved CuCoordSphereCu3P.tif

File:P73- structure.svg

File:16293-ICSDzoom.png

Polyphosphides contain {{chem2|P\sP}} bonds. The simplest polyphosphides would be derivatives of {{chem|P|2|4-}}. The free anions are rarely encountered because they are so basic. Most members follow the octet rule.

Well studied polyphosphides are derivatives of {{chem|P|7|3-}}.{{cite journal |doi=10.1002/zaac.19875520907 |title=Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 44. Tricäsiumheptaphosphid Cs₃P₇: Darstellung, Struktur und Eigenschaften |date=1987 |last1=Meyer |first1=Teodoro |last2=Hönle |first2=Wolfgang |last3=von Schnering |first3=Hans Georg |journal=Zeitschrift für Anorganische und Allgemeine Chemie |volume=552 |issue=9 |pages=69–80 }}

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-{{chem|P|6|6-}} subunits.{{cite journal |last1=Gullman |first1=Jan |last2=Olofsson |first2=Olle |title=The crystal structure of SnP₃ and a note on the crystal structure of GeP₃ |journal=Journal of Solid State Chemistry |date=1 November 1972 |volume=5 |issue=3 |pages=441–445 |doi=10.1016/0022-4596(72)90091-6 |url=https://www.sciencedirect.com/science/article/abs/pii/0022459672900916 |access-date=28 March 2024 |issn=0022-4596}} Another example of deceptive nomenclature is "thorium pentaphosphide", which consists of a polymeric polyphosphide related to Hittorf's phosphorus.{{cite journal |doi=10.3891/acta.chem.scand.25-1327 |title=The Crystal Structure of TlP₅ |date=1971 |last1=Olofsson |first1=Olle |last2=Gullman |first2=Jan |last3=Søtofte |first3=Inger |last4=Beronius |first4=P. |last5=Engebretsen |first5=Jan E. |last6=Ehrenberg |first6=L. |journal=Acta Chemica Scandinavica |volume=25 |pages=1327–1337 }}

Several polyphosphides contain the cluster {{chem|P|11|3-}} ions and polymeric chain anions (e.g. the helical {{chem|(|P|-|)|n}} ion) and complex sheet or 3-D anions.{{Cite journal | doi = 10.1080/03086648708080608| title = Phosphides and Polyphosphides of the Transition Metals| journal = Phosphorus and Sulfur and the Related Elements| volume = 30| issue = 1–2| pages = 413–416| year = 1987| last1 = Jeitschko | first1 = W. | last2 = Möller | first2 = M. H. }} The range of structures is extensive. Potassium has nine phosphides: {{chem2|K3P}}, {{chem2|K4P3}}, {{chem2|K5P4}}, {{chem2|KP}}, {{chem2|K4P6}}, {{chem2|K3P7}}, {{chem2|K3P11}}, {{chem2|KP10.3}}, {{chem2|KP15}}. Eight mono- and polyphosphides of nickel also exist: ({{chem2|Ni3P}}, {{chem2|Ni5P2}}, {{chem2|Ni12P5}}, {{chem2|Ni2P}}, {{chem2|Ni5P4}}, {{chem2|NiP}}, {{chem2|NiP2}}, {{chem2|NiP3}}).

Two polyphosphide ions, {{chem|P|3|4-}} found in {{chem|K|4|P|3}} and {{chem|P|4|5-}} found in {{chem2|K5P4}}, are radical anions with an odd number of valence electrons.

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.{{cite journal | last1 = von Schnering |first1 = Hans-Georg | last2 = Hönle | first2=Wolfgang | title = Bridging Chasms with Phosphides | journal = Chemical Reviews | year = 1988 | volume = 88 | pages = 243–273 | doi = 10.1021/cr00083a012}} Hydrothermal reactions to generate nickel phosphides have produced pure and well crystallized nickel phosphide compounds, {{chem2|Ni2P}} and {{chem2|Ni12P5}}. These compounds were synthesized through a solid-liquid reaction between {{chem2|NiCl2*12H2O}} and red phosphorus at 200 °C for 24 and 48 hours, respectively.{{cite journal | author1 = Liu, Zongyi | author2 = Huang, Xiang | author3 = Zhu, Zhibin | author4 = Dai, Jinhui | title = A simple mild hydrothermal route for the synthesis of nickel phosphide powders | journal = Ceramics International | volume = 36 | year = 2010 | pages = 1155–1158 | doi = 10.1016/j.ceramint.2009.12.015 | issue = 3}}

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.

File:MoP NR2 3.svg A method for the preparation of {{chem2|K2P16}} from red phosphorus and potassium ethoxide has been reported.{{cite journal|title=Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide|first1=Alina|last1=Dragulescu-Andrasi|first2=L. Zane|last2=Miller|first3=Banghao|last3=Chen|first4=D. Tyler |last4=McQuade|first5=Michael|last5=Shatruk|journal= Angewandte Chemie International Edition|date=March 14, 2016|volume=55|issue=12|pages=3904–3908|doi=10.1002/anie.201511186|pmid=26928980|doi-access=free}}

Compounds with triple bonds between a metal and phosphorus are rare. The main examples have the formula {{chem2|P\tMo(NR2)3}}, where R is a bulky organic substituent.{{Cite journal | doi = 10.1021/cr9003709| pmid = 20175534| title = Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus| journal = Chemical Reviews| volume = 110| issue = 7| pages = 4164–77| year = 2010| last1 = Cossairt | first1 = B. M. | last2 = Piro | first2 = N. A. | last3 = Cummins | first3 = C. C. | citeseerx = 10.1.1.666.8019}}

{{See also|Phosphaalkyne}}

Many organophosphides are known. Common examples have the formula {{chem2|R2PM}} where R is an organic substituent and M is a metal. One example is lithium diphenylphosphide. The Zintl cluster {{chem|P|7|3-}} is obtained with diverse alkali metal derivatives.

The mineral schreibersite {{chem2|(Fe,Ni)3P}} is common in some meteorites.

{{Reflist|2}}

{{Phosphides}}

{{Monatomic anion compounds}}

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Category:Anions

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Category:Phosphorus(−III) compounds