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Diphosphorus is an
inorganic In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistr ...
chemical with the chemical formula . Unlike nitrogen, its lighter pnictogen neighbor which forms a stable N2 molecule with a nitrogen to nitrogen
triple bond A triple bond in chemistry is a chemical bond between two atoms involving six bonding electrons instead of the usual two in a covalent single bond. Triple bonds are stronger than the equivalent single bonds or double bonds, with a bond order o ...
, phosphorus prefers a tetrahedral form P4 because P-P pi-bonds are high in energy. Diphosphorus is, therefore, very reactive with a
bond-dissociation energy The bond-dissociation energy (BDE, ''D''0, or ''DH°'') is one measure of the strength of a chemical bond . It can be defined as the standard enthalpy change when is cleaved by homolysis to give fragments A and B, which are usually radical s ...
(117
kcal The calorie is a unit of energy. For historical reasons, two main definitions of "calorie" are in wide use. The large calorie, food calorie, or kilogram calorie was originally defined as the amount of heat needed to raise the temperature of o ...
/ mol or 490 kJ/mol) half that of dinitrogen. The bond distance has been measured at 1.8934 Å.


Synthesis

Diphosphorus has been generated by heating white phosphorus at 1100 kelvins (827
°C The degree Celsius is the unit of temperature on the Celsius scale (originally known as the centigrade scale outside Sweden), one of two temperature scales used in the International System of Units (SI), the other being the Kelvin scale. The d ...
). Nevertheless, some advancements have been obtained in generating the diatomic molecule in homogeneous solution under normal conditions with the use of some
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
complexes (based on, for example, tungsten and
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has si ...
). Methods for dissociation of bonds in P4 molecules via
photoexcitation Photoexcitation is the production of an excited state of a quantum system by photon absorption. The excited state originates from the interaction between a photon and the quantum system. Photons carry energy that is determined by the wavelengths ...
were also proposed. The molecule attracted attention in 2006, when a new method for its synthesis at milder temperatures emerged. This method is a variation on nitrogen expulsion in
azide In chemistry, azide is a linear, polyatomic anion with the formula and structure . It is the conjugate base of hydrazoic acid . Organic azides are organic compounds with the formula , containing the azide functional group. The dominant applic ...
s with formation of a nitrene. The synthesis of the diphosphorus precursor consists of reacting a terminal
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has si ...
phosphide In chemistry, a phosphide is a compound containing the 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 phos ...
with a chloroiminophosphane: : Heating this compound at 50 °C in
1,3-cyclohexadiene Cyclohexa-1,3-diene is an organic compound with the formula (C2H4)(CH)4. It is a colorless, flammable liquid. Its refractive index is 1.475 (20 °C, D). A naturally occurring derivative of 1,3-cyclohexadiene is terpinene, a component of pine oi ...
serving as a solvent and as a
trapping reagent In chemistry, a chemical trap is a chemical compound that is used to detect unstable compounds. The method relies on efficiency of bimolecular reactions with reagents to produce a more easily characterize trapped product. In some cases, the trappin ...
expels diphosphorus, which is reactive, as the end products are a double Diels–Alder adduct and the niobium imido compound: : The same imido compound also forms when the
thermolysis Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is re ...
is performed in toluene, but in this case the fate of the diphosphorus is unknown. P2 has been suggested to form as an intermediate in the photolysis of P4, and in the presence of 2,3-dimethyl-1,3-butadiene the diphosphane resulting from Diels–Alder addition is again formed. To date, no direct evidence of P2 formation via P4 photolysis exists. The generation of diphosphorus from a diphosphorus bisanthracene adduct has been reported. The synthesis of a stabilized HP2+ cation has been reported.


References


External links

*Ron Dagani, "A Mild Route To P2", ''
Chemical & Engineering News ''Chemical & Engineering News'' (''C&EN'') is a weekly news magazine published by the American Chemical Society, providing professional and technical news and analysis in the fields of chemistry and chemical engineering.Link
*Carmen Drahl "Flash Of Phosphorus Chemistry Innovation", ''
Chemical & Engineering News ''Chemical & Engineering News'' (''C&EN'') is a weekly news magazine published by the American Chemical Society, providing professional and technical news and analysis in the fields of chemistry and chemical engineering.Link
{{diatomicelements Phosphorus Homonuclear diatomic molecules