Diphosphane

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Diphosphane
Stereo structural formula of diphosphane with explicit hydrogens Diphosphan.svg
Stereo structural formula of diphosphane with explicit hydrogens
Ball-and-stick model of diphosphane Diphosphane-3D-balls.png
Ball-and-stick model of diphosphane
Names
IUPAC name
Diphosphane
Systematic IUPAC name
Diphosphane (substitutive)
Tetrahydridodiphosphorus(PP) (additive)
Other names
Diphosphine
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/H4P2/c1-2/h1-2H2 X mark.svgN
    Key: VURFVHCLMJOLKN-UHFFFAOYSA-N X mark.svgN
  • PP
Properties
H4P2
Molar mass 65.980 g·mol−1
Melting point −99 °C (−146 °F; 174 K)
Boiling point 63.5 °C (146.3 °F; 336.6 K) (Extrapolated, decomposes)
Related compounds
Other anions
ammonia
hydrazine
triazane
Other cations
diphosphines
Related Binary Phosphorus halides
diphosphorus tetrafluoride
diphosphorus tetrachloride
diphosphorus tetrabromide
diphosphorus tetraiodide
Related compounds
phosphane
triphosphane
diphosphene
diphosphenes
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Diphosphane, or diphosphine, is an inorganic compound with the chemical formula P2H4. This colourless liquid is one of several binary phosphorus hydrides. It is the impurity that typically causes samples of phosphine to ignite in air.

Contents

Properties, preparation, reactions

Diphosphane adopts the gauche conformation (like hydrazine, less symmetrical than shown in the image) with a P−P distance of 2.219 angstroms. It is nonbasic, unstable at room temperature, and spontaneously flammable in air. It is only poorly soluble in water but dissolves in organic solvents. Its 1H NMR spectrum consists of 32 lines resulting from an A2XX'A'2 splitting system. [1]

Diphosphane is produced by the hydrolysis of calcium monophosphide, which can be described as the Ca2+ derivative of P4−2. According to an optimized procedure, hydrolysis of 400 g of CaP at −30 °C gives about 20 g of product, slightly contaminated with phosphine.

Reaction of diphosphane with butyllithium affords a variety of condensed polyphosphine compounds.

Organic diphosphanes

A variety of organic derivatives of diphosphane are known, but asymmetric diphosphanes are only stable at cryogenic temperatures. Otherwise, the substituents facily redistribute on the phosphorus centers to give a mixture of products. On the other hand, there appears to be a substantial barrier to chiral inversion. [2]

The central bond is weak, and easily adds substituents. [3]

The simplest synthesis method heats a phosphorus halide and a phosphane:

Ph2PCl + HPPh2 → Ph2P-PPh2 + HCl↑

Alkali metals can replace the hydrogen in that reaction (i.e., a dialkylphosphide), and in some rare cases a dialkylamine can replace the halide. Symmetric diphosphanes are easily prepared by reductive coupling, e.g. tetraphenyldiphosphine from chlorodiphenylphosphine:

2 ClPPh2 + 2 Na → Ph2P−PPh2 + 2 NaCl

Ultraviolet radiation decomposes mercury(II) dialkylphosphides to the metal and a dialkylphosphane. [4]

The methyl compound P2Me4 is prepared by the reduction of Me2P(S)−P(S)Me2, which is produced by methylation of thiophosphoryl chloride with methylmagnesium bromide. [5]

See also

Related Research Articles

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

<span class="mw-page-title-main">Phosphonium</span> Family of polyatomic cations containing phosphorus

In chemistry, the term phosphonium describes polyatomic cations with the chemical formula PR+
4
. These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions.

In organic chemistry, the Wurtz reaction, named after Charles Adolphe Wurtz, is a coupling reaction whereby two alkyl halides are treated with sodium metal to form a higher alkane.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Organotin chemistry</span> Branch of organic chemistry

Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin–carbon bonds. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

<span class="mw-page-title-main">Phosphide</span>

In chemistry, a phosphide is a compound containing the P3− ion or its equivalent. Many different phosphides are known, with widely differing structures. 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. Finally, some phosphides are molecular.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

<span class="mw-page-title-main">Phosphine oxide</span> Class of chemical compounds

Phosphine oxides are phosphorus compounds with the formula OPX3. When X = alkyl or aryl, these are organophosphine oxides. Triphenylphosphine oxide is an example. An inorganic phosphine oxide is phosphoryl chloride (POCl3).

<span class="mw-page-title-main">Phosphinite</span> Organic compounds of the formula P(OR)R2

In organic chemistry, phosphinites are organophosphorus compounds with the formula P(OR)R2. They are used as ligands in homogeneous catalysis and coordination chemistry.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">1,1'-Bis(diphenylphosphino)ferrocene</span> Chemical compound

1,1-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an organophosphorus compound commonly used as a ligand in homogeneous catalysis. It contains a ferrocene moiety in its backbone, and is related to other bridged diphosphines such as 1,2-bis(diphenylphosphino)ethane (dppe).

Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fungicides. In general these applications are declining in step with growing concerns about their impact on the environment and human health. The parent compounds are arsane and arsenic acid. Despite their toxicity, organoarsenic biomolecules are well known.

<span class="mw-page-title-main">Diphosphine ligands</span>

Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts.

<span class="mw-page-title-main">Diphenylphosphine</span> Chemical compound

Diphenylphosphine, also known as diphenylphosphane, is an organophosphorus compound with the formula (C6H5)2PH. This foul-smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as catalysts.

Oxophilicity is the tendency of certain chemical compounds to form oxides by hydrolysis or abstraction of an oxygen atom from another molecule, often from organic compounds. The term is often used to describe metal centers, commonly the early transition metals such as titanium, niobium, and tungsten. Oxophilicity is often stated to be related to the hardness of the element, within the HSAB theory, but it has been shown that oxophilicity depends more on the electronegativity and effective nuclear charge of the element than on its hardness. This explains why the early transition metals, whose electronegativities and effective nuclear charges are low, are very oxophilic. Many main group compounds are also oxophilic, such as derivatives of aluminium, silicon, and phosphorus(III). The handling of oxophilic compounds often requires air-free techniques.

<span class="mw-page-title-main">Sodium selenide</span> Chemical compound

Sodium selenide is an inorganic compound of sodium and selenium with the chemical formula Na2Se.

<span class="mw-page-title-main">Carbonyl reduction</span> Organic reduction of any carbonyl group by a reducing agent

In organic chemistry, carbonyl reduction is the conversion of any carbonyl group, usually to an alcohol. It is a common transformation that is practiced in many ways. Ketones, aldehydes, carboxylic acids, esters, amides, and acid halides - some of the most pervasive functional groups, -comprise carbonyl compounds. Carboxylic acids, esters, and acid halides can be reduced to either aldehydes or a step further to primary alcohols, depending on the strength of the reducing agent. Aldehydes and ketones can be reduced respectively to primary and secondary alcohols. In deoxygenation, the alcohol group can be further reduced and removed altogether by replacement with H.

<span class="mw-page-title-main">Polysilane</span>

Polysilanes are organosilicon compounds with the formula (R2Si)n. They are relatives of traditional organic polymers but their backbones are composed of silicon atoms. They exhibit distinctive optical and electrical properties. They are mainly used as precursors to silicon carbide. The simplest polysilane would be (SiH2)n, which is mainly of theoretical, not practical interest.

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

References

  1. Marianne Baudler, Klaus Glinka (1993). "Monocyclic and polycyclic phosphines". Chem. Rev. 93 (4): 1623–1667. doi:10.1021/cr00020a010.
  2. Phosphorus: Chemistry, Biochemistry and Technology, Sixth Edition, 2013, D.E.C. Corbridge, CRC Pres, Taylor Francis Group, ISBN   978-1-4398-4088-7. pp. 421-422.
  3. Corbridge 2013, p. 422.
  4. Corbridge 2013, pp. 421–422.
  5. Butter, S. A.; Chatt, J. (1974). "Ethylenebis(dimethylphosphine)". Inorg. Synth. 15: 185. doi:10.1002/9780470132463.ch41. ISBN   9780470132463.