Phosphorus pentachloride

The structures for the phosphorus chlorides are invariably consistent with VSEPR theory. The structure of PCl₅ depends on its environment. Gaseous and molten PCl₅ is a neutral molecule with trigonal bipyramidal geometry and (D_3h) symmetry. The hypervalent nature of this species (as well as of PCl⁻
₆, see below) can be explained with the inclusion of non-bonding molecular orbitals (molecular orbital theory) or resonance (valence bond theory). This trigonal bipyramidal structure persists in nonpolar solvents, such as CS₂ and CCl₄.^[5] In the solid state PCl₅ is an ionic compound called tetrachlorophosphonium hexachlorophosphate formulated PCl⁺
₄PCl⁻
₆.^[6]

In solutions of polar solvents, PCl₅ undergoes self-ionization.^[8] Dilute solutions dissociate according to the following equilibrium:

PCl₅ ⇌ PCl⁺
₄ + Cl⁻

At higher concentrations, a second equilibrium becomes more prevalent:

2 PCl₅ ⇌ PCl⁺
₄ + PCl⁻
₆

The cation PCl⁺
₄ and the anion PCl⁻
₆ are tetrahedral and octahedral, respectively. At one time, PCl₅ in solution was thought to form a dimeric structure, P₂Cl₁₀, but this suggestion is not supported by Raman spectroscopic measurements.

AsCl₅ and SbCl₅ also adopt trigonal bipyramidal structures. The relevant bond distances are 211 pm (As−Cl_eq), 221 pm (As−Cl_ax), 227 pm (Sb−Cl_eq), and 233.3 pm (Sb−Cl_ax).^[9] At low temperatures, SbCl₅ converts to the dimer, dioctahedral Sb₂Cl₁₀, structurally related to niobium pentachloride.

PCl₅ is prepared by the chlorination of PCl₃.^[10] This reaction is used to produce around 10,000 tonnes of PCl₅ per year (as of 2000).^[6]

PCl₃ + Cl₂ ⇌ PCl₅   (ΔH = −124 kJ/mol)

PCl₅ exists in equilibrium with PCl₃ and chlorine, and at 180 °C the degree of dissociation is about 40%.^[6] Because of this equilibrium, samples of PCl₅ often contain chlorine, which imparts a greenish coloration.

In its most characteristic reaction, PCl₅ reacts upon contact with water to release hydrogen chloride and give phosphorus oxides. The first hydrolysis product is phosphorus oxychloride:

PCl₅ + H₂O → POCl₃ + 2 HCl

In hot water, hydrolysis proceeds completely to orthophosphoric acid:

PCl₅ + 4 H₂O → H₃PO₄ + 5 HCl

Phosphorus pentachloride is a Lewis acid. This property underpins many of its characteristic reactions, autoionization, chlorinations, hydrolysis. A well studied adduct is PCl₅(pyridine).^[11]

In synthetic chemistry, two classes of chlorination are usually of interest: oxidative chlorinations and substitutive chlorinations. Oxidative chlorinations entail the transfer of Cl₂ from the reagent to the substrate. Substitutive chlorinations entail replacement of O or OH groups with chloride. PCl₅ can be used for both processes.

Upon treatment with PCl₅, carboxylic acids convert to the corresponding acyl chloride.^[12] The following mechanism has been proposed:^[13]

It also converts alcohols to alkyl chlorides. Thionyl chloride is more commonly used in the laboratory because the resultant sulfur dioxide is more easily separated from the organic products than is POCl₃.

PCl₅ reacts with a tertiary amides, such as dimethylformamide (DMF), to give dimethylchloromethyleneammonium chloride, which is called the Vilsmeier reagent, [(CH₃)₂N=CClH]Cl. More typically, a related salt is generated from the reaction of DMF and POCl₃. Such reagents are useful in the preparation of derivatives of benzaldehyde by formylation and for the conversion of C−OH groups into C−Cl groups.^[14]

It is especially renowned for the conversion of C=O groups to CCl₂ groups.^[15] For example, benzophenone and phosphorus pentachloride react to give the diphenyldichloromethane:^[16]

(C₆H₅)₂CO + PCl₅ → (C₆H₅)₂CCl₂ + POCl₃

The electrophilic character of PCl₅ is highlighted by its reaction with styrene to give, after hydrolysis, phosphonic acid derivatives.^[17]

Both PCl₃ and PCl₅ convert R₃COH groups to the chloride R₃CCl. The pentachloride is however a source of chlorine in many reactions. It chlorinates allylic and benzylic CH bonds. PCl5 bears a greater resemblance to SO₂Cl₂, also a source of Cl₂. For oxidative chlorinations on the laboratory scale, sulfuryl chloride is often preferred over PCl₅ since the gaseous SO₂ by-product is readily separated.

As for the reactions with organic compounds, the use of PCl₅ has been superseded by SO₂Cl₂. The reaction of phosphorus pentoxide and PCl₅ produces POCl₃ :^{[18][page needed]}

6 PCl₅ + P₄O₁₀ → 10 POCl₃

PCl₅ chlorinates nitrogen dioxide to form unstable nitryl chloride:

PCl₅ + 2 NO₂ → PCl₃ + 2 NO₂Cl

2 NO₂Cl → 2 NO₂ + Cl₂

PCl₅ is a precursor for lithium hexafluorophosphate, LiPF₆. Lithium hexafluorophosphate is a commonly employed salt in electrolytes in lithium ion batteries.^[19] LiPF
₆ is produced by the reaction of PCl
₅ with lithium fluoride, with lithium chloride as a side product:

PCl₅ + 6 LiF → LiPF₆ + 5 LiCl

PCl₅ is a dangerous substance as it reacts violently with water. It is also corrosive when in contact with skin and can be fatal when inhaled.

Phosphorus pentachloride was first prepared in 1808 by the English chemist Humphry Davy.^[20] Davy's analysis of phosphorus pentachloride was inaccurate;^[21] the first accurate analysis was provided in 1816 by the French chemist Pierre Louis Dulong.^[22]

• Phosphorus halides
• Phosphorus trichloride
• Phosphoryl chloride
• Phosphorus trifluorodichloride

• The period 3 chlorides
• International Chemical Safety Card 0544
• CDC - NIOSH Pocket Guide to Chemical Hazards