Phosphorus pentafluoride is a chemical compound with the

chemical formula A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as pare ...

. It is a phosphorus halide. It is a colourless, toxic gas that fumes in air.

Preparation

Phosphorus pentafluoride was first prepared in 1876 by the fluorination of

phosphorus pentachloride Phosphorus pentachloride is the chemical compound with the formula . It is one of the most important phosphorus chlorides/oxychlorides, others being and . finds use as a chlorinating reagent. It is a colourless, water-sensitive solid, althoug ...

using arsenic trifluoride, which remains a favored method: : Phosphorus pentafluoride can be prepared by direct combination of

phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...

and

fluorine Fluorine is a chemical element; it has Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard temperature and pressure, standard conditions as pale yellow Diatomic molecule, diatomic gas. Fluorine is extre ...

: :

Structure

Single-crystal X-ray studies indicate that the has trigonal bipyramidal geometry. Thus it has two distinct types of P−F bonds (axial and equatorial): the length of an axial P−F bond is distinct from the equatorial P−F bond in the solid phase, but not the liquid or gas phases due to Berry pseudo rotation. Fluorine-19 NMR spectroscopy, even at temperatures as low as , fails to distinguish the axial from the equatorial fluorine environments. The apparent equivalency arises from the low barrier for pseudorotation via the

Berry mechanism The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerization, isomerize by exchanging the two axial ligands (see the figure) for two of the equatorial ones. It is the most ...

, by which the axial and equatorial fluorine atoms rapidly exchange positions. The apparent equivalency of the F centers in was first noted by Gutowsky. The explanation was first described by R. Stephen Berry, after whom the Berry mechanism is named. Berry pseudorotation influences the ¹⁹F

NMR Nuclear magnetic resonance (NMR) is a physical phenomenon in which atomic nucleus, nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near and far field, near field) and respond by producing ...

spectrum of since NMR spectroscopy operates on a

millisecond A millisecond (from '' milli-'' and second; symbol: ms) is a unit of time in the International System of Units equal to one thousandth (0.001 or 10−3 or 1/1000) of a second or 1000 microseconds. A millisecond is to one second, as one second i ...

timescale. Electron diffraction and X-ray crystallography do not detect this effect as the solid state structures are, relative to a molecule in solution, static and can not undergo the necessary changes in atomic position.

Lewis acidity

Phosphorus pentafluoride is a

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...

. This property is relevant to its ready hydrolysis. A well studied

adduct In chemistry, an adduct (; alternatively, a contraction of "addition product") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all components. The resultant is ...

is with

pyridine Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom . It is a highly flammable, weak ...

. With primary and secondary

amines In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...

, the adducts convert readily to dimeric amino-bridged derivatives with the formula . A variety of complexes are known with bidentate

ligands In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's ...

. Hexafluorophosphoric acid () is derived from phosphorus pentafluoride and

hydrogen fluoride Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...

. Its conjugate base,

hexafluorophosphate Hexafluorophosphate is an fluoroanion, anion with chemical formula of . It is an Octahedral molecular geometry, octahedral species that imparts no color to its salts. is isoelectronic with sulfur hexafluoride, , and the Hexafluorosilicic acid, h ...

(), is a useful

non-coordinating anion Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly foun ...

. It is often used in

lithium-ion batteries A lithium-ion or Li-ion battery is a type of rechargeable battery that uses the reversible intercalation of Li+ ions into electronically conducting solids to store energy. Li-ion batteries are characterized by higher specific energy, energy ...

, where besides providing good ionic conductivity for the liquid electrolyte, it also passivates positive

aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...

current collector.

References

{{fluorine compounds Phosphorus(V) compounds Phosphorus fluorides