“Phosphide”的意思、由来-开放百科全书

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.

Binary monophosphides

Examples of group 1 include {{chem|link=sodium phosphide|Na|3|P}}. Notable examples include aluminium phosphide , zinc phosphide , calcium phosphide exploiting their tendency to release toxic phosphine upon hydrolysis. Magnesium phosphide (Mg₃P₂) also is moisture sensitive. Indium phosphide (InP) and GaP are used as a semi-conductors, often in combination of related arsenides.^[3] Copper phosphide (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:

Polyphosphides

Two polyphosphide ions, {{chem|P|3|4-}} found in {{chem|K|4|P|3}} and {{chem|P|4|5-}} found in K₅P₄, are radical anions with an odd number of valence electrons making both compounds paramagnetic.^[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.^[5] Hydrothermal reactions to generate nickel phosphides have produced pure and well crystallized nickel phosphide compounds, Ni₂P and Ni₁₂P₅. These compounds were synthesized through a solid-liquid reaction between NiCl₂∙12H₂O and red phosphorus at 200 °C for 24 and 48 hours, respectively.^[6]

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.

Molecular phosphides

Compounds with triple bonds between a metal and phosphorus are rare. The main examples have the formula Mo(P)(NR₂)₃, where R is a bulky organic substituent.^[8]

Organic phosphides

Many organophosphides are known. Common examples have the formular 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.

Natural examples

References

1. ^{{Greenwood&Earnshaw}}
2. ^¹²Von 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. ^{{Cite journal | doi = 10.1039/b304084b| title = Chemical vapour deposition of group Vb metal phosphide thin films| journal = Journal of Materials Chemistry| volume = 13| issue = 8| pages = 1930| year = 2003| last1 = Blackman | first1 = C. S.| last2 = Carmalt | first2 = C. J.| last3 = O'Neill | first3 = S. A.| last4 = Parkin | first4 = I. P.| last5 = Molloy | first5 = K. C.| last6 = Apostolico | first6 = L.| url = http://discovery.ucl.ac.uk/143120/1/Blackman_Group_VB_2_Corrected.pdf}}
4. ^{{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. }}
5. ^{{cite journal | author1 = von Schnering, Hans-Georg | author2 = Hönle, Wolfgang | title = Bridging Chasms with Phosphides | journal = Chem. Rev. | year = 1988 | volume = 88 | pages = 243–273 | doi = 10.1021/cr00083a012}}
6. ^{{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}}
7. ^Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide A. Dragulescu-Andrasi, L. Z. Miller, B. Chen, D. T. McQuade, M. Shatruk, Angew. Chem. Int. Ed. 2016, 55, 3904.{{doi|10.1002/anie.201511186}}
8. ^{{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}}