Phosphorus trifluoride

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Phosphorus trifluoride
Structure and dimensions of phosphorus trifluoride Phosphorus-trifluoride-2D-dimensions.png
Structure and dimensions of phosphorus trifluoride
Space-filling model of phosphorus trifluoride Phosphorus-trifluoride-3D-vdW.png
Space-filling model of phosphorus trifluoride
Names
IUPAC names
Phosphorus trifluoride
Phosphorus(III) fluoride
Trifluorophosphane
Trifluoridophosphorus
Perfluorophosphane
Other names
Trifluorophosphine
Phosphorous fluoride
TL-75
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.029.098 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • TH3850000
UNII
  • InChI=1S/F3P/c1-4(2)3 Yes check.svgY
    Key: WKFBZNUBXWCCHG-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/F3P/c1-4(2)3
    Key: WKFBZNUBXWCCHG-UHFFFAOYAK
  • FP(F)F
Properties
PF3
Molar mass 87.968971 g/mol
Appearancecolorless gas
Density 3.91 g/L, gas
Melting point −151.5 °C (−240.7 °F; 121.6 K)
Boiling point −101.8 °C (−151.2 °F; 171.3 K)
slow hydrolysis
Structure
Trigonal pyramidal
1.03 D
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
0
1
Flash point Non-flammable
Related compounds
Other anions
Phosphorus trichloride
Phosphorus tribromide
Phosphorus triiodide
Phosphane
Other cations
Nitrogen trifluoride
Arsenic trifluoride
Antimony trifluoride
Bismuth trifluoride
Related ligands
Carbon monoxide
Related compounds
 Phosphorus pentafluoride
Supplementary data page
Phosphorus trifluoride (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Phosphorus trifluoride (formula P F 3), is a colorless and odorless gas. It is highly toxic and reacts slowly with water. Its main use is as a ligand in metal complexes. As a ligand, it parallels carbon monoxide in metal carbonyls, [1] and indeed its toxicity is due to its binding with the iron in blood hemoglobin in a similar way to carbon monoxide.

Contents

Physical properties

Phosphorus trifluoride has an F−P−F bond angle of approximately 96.3°. Gaseous PF3 has a standard enthalpy of formation of −945 kJ/mol (−226  kcal/mol). The phosphorus atom has a nuclear magnetic resonance chemical shift of 97 ppm (downfield of H3PO4).

Properties

Phosphorus trifluoride hydrolyzes especially at high pH, but it is less hydrolytically sensitive than phosphorus trichloride. It does not attack glass except at high temperatures, and anhydrous potassium hydroxide may be used to dry it with little loss. With hot metals, phosphides and fluorides are formed. With Lewis bases such as ammonia addition products (adducts) are formed, and PF3 is oxidized by oxidizing agents such as bromine or potassium permanganate.

As a ligand for transition metals, PF3 is a strong π-acceptor. [2] It forms a variety of metal complexes with metals in low oxidation states. PF3 forms several complexes for which the corresponding CO derivatives (see metal carbonyl) are unstable or nonexistent. Thus, Pd(PF3)4 is known, but Pd(CO)4 is not. [3] [4] [5] Such complexes are usually prepared directly from the related metal carbonyl compound, with loss of CO. However, nickel metal reacts directly with PF3 at 100 °C under 35 MPa pressure to form Ni(PF3)4, which is analogous to Ni(CO)4. Cr(PF3)6, the analogue of Cr(CO)6, may be prepared from dibenzenechromium:

Cr(C6H6)2 + 6 PF3 → Cr(PF3)6 + 2 C6H6
Tetrakis(trifluorophosphine)platinum(0)-from-xtal-2008-3D-balls.png Tetrakis(trifluorophosphine)platinum(0)-from-xtal-2008-3D-SF.png
Ball-and-stick model of [Pt(PF3)4] Space-filling model of [Pt(PF3)4]

Preparation

Phosphorus trifluoride is usually prepared from phosphorus trichloride via halogen exchange using various fluorides such as hydrogen fluoride, calcium fluoride, arsenic trifluoride, antimony trifluoride, or zinc fluoride: [6] [7] [8]

2 PCl3 + 3 ZnF2 → 2 PF3 + 3 ZnCl2

Biological activity

Phosphorus trifluoride is similar to carbon monoxide in that it is a gas which strongly binds to iron in hemoglobin, preventing the blood from absorbing oxygen.

Precautions

PF3 is highly toxic, comparable to phosgene. [9]

Related Research Articles

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

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

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

Chlorine pentafluoride is an interhalogen compound with formula ClF5. This colourless gas is a strong oxidant that was once a candidate oxidizer for rockets. The molecule adopts a square pyramidal structure with C4v symmetry, as confirmed by its high-resolution 19F NMR spectrum. It was first synthesized in 1963.

<span class="mw-page-title-main">Chromium(III) fluoride</span> Chemical compound

Chromium(III) fluoride is an inorganic compound with the chemical formula CrF3. It forms several hydrates. The compound CrF3 is a green crystalline solid that is insoluble in common solvents, but the hydrates [Cr(H2O)6]F3 (violet) and [Cr(H2O)6]F3·3H2O (green) are soluble in water. The anhydrous form sublimes at 1100–1200 °C.

<span class="mw-page-title-main">Iron(III) fluoride</span> Chemical compound

Iron(III) fluoride, also known as ferric fluoride, are inorganic compounds with the formula FeF3(H2O)x where x = 0 or 3. They are mainly of interest by researchers, unlike the related iron(III) chloride. Anhydrous iron(III) fluoride is white, whereas the hydrated forms are light pink.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

Carbonyl fluoride is a chemical compound with the formula COF2. It is a carbon oxohalide. This gas, like its analog phosgene, is colourless and highly toxic. The molecule is planar with C2v symmetry, bond lengths of 1.174 Å (C=O) and 1.312 Å (C–F), and an F–C–F bond angle of 108.0°.

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

Phosphorus trioxide is the chemical compound with the molecular formula P4O6. Although the molecular formula suggests the name tetraphosphorus hexoxide, the name phosphorus trioxide preceded the knowledge of the compound's molecular structure, and its usage continues today. This colorless solid is structurally related to adamantane. It is formally the anhydride of phosphorous acid, H3PO3, but cannot be obtained by the dehydration of the acid. A white solid that melts at room temperature, it is waxy, crystalline and highly toxic, with garlic odor.

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

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO2+ center.

<span class="mw-page-title-main">Metal nitrosyl complex</span> Complex of a transition metal bonded to nitric oxide: Me–NO

Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.

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

Phosphorus pentafluoride, PF5, is a phosphorus halide. It is a colourless, toxic gas that fumes in air.

Diboron tetrafluoride is the inorganic compound with the formula (BF2)2. A colorless gas, the compound has a halflife of days at room temperature. It is the most stable of the diboron tetrahalides, and does not appreciably decompose under standard conditions.

Boron monofluoride or fluoroborylene is a chemical compound with the formula BF, one atom of boron and one of fluorine. It is an unstable gas, but it is a stable ligand on transition metals, in the same way as carbon monoxide. It is a subhalide, containing fewer than the normal number of fluorine atoms, compared with boron trifluoride. It can also be called a borylene, as it contains boron with two unshared electrons. BF is isoelectronic with carbon monoxide and dinitrogen; each molecule has 14 electrons.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

<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).

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

Rhodium(III) fluoride or rhodium trifluoride is the inorganic compound with the formula RhF3. It is a red-brown, diamagnetic solid.

<span class="mw-page-title-main">Chromium(II) iodide</span> Chemical compound

Chromium(II) iodide is the inorganic compound with the formula CrI2. It is a red-brown or black solid. The compound is made by thermal decomposition of chromium(III) iodide. Like many metal diiodides, CrI2 adopts the "cadmium iodide structure" motif, i.e., it features sheets of octahedral Cr(II) centers interconnected by bridging iodide ligands. Reflecting the effects of its d4 configuration, chromium's coordination sphere is highly distorted.

<span class="mw-page-title-main">Rhodium(III) bromide</span> Chemical compound

Rhodium(III) bromide refers to inorganic compounds of the formula RhBr3(H2O)n where n = 0 or approximately three. Both forms are brown solids. The hydrate is soluble in water and lower alcohols. It is used to prepare rhodium bromide complexes. Rhodium bromides are similar to the chlorides, but have attracted little academic or commercial attention.

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

Potassium tetracyanonickelate (IUPAC: Potassium tetracyanido nickelate(II)) is the inorganic compound with the formula K2Ni(CN)4. It is usually encountered as the monohydrate but the anhydrous salt is also known. Both are yellow, water-soluble, diamagnetic solids. The salt consists of potassium ions and the tetracyanonickelate coordination complex, which is square planar. The [Ni(CN)4]2- anions are arranged in a columnar structure with Ni---Ni distances of 4.294 Å, which is well beyond the sum of the van der Waals radius of the nickel cation. This columnar structure resembles those of the other [M(CN)4]2- anions of the heavy congeners of the group 10 metals (M = Pd, Pt).

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +4, and +3 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. The tetrathioperrhenate anion [ReS4]− is possible.

References

  1. ↑ Chatt, J. (1950). "The Co-Ordinate Link in Chemistry". Nature. 165 (4199): 637–638. Bibcode:1950Natur.165..637C. doi:10.1038/165637a0. PMID   15416738.
  2. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 494. ISBN   978-0-08-037941-8.
  3. ↑ Nicholls, D. (1973). Complexes and First-Row Transition Elements. London: Macmillan Press.
  4. ↑ Kruck, T. (1967). "Trifluorphosphin-Komplexe von Übergangsmetallen". Angewandte Chemie. 79 (1): 27–43. Bibcode:1967AngCh..79...27K. doi:10.1002/ange.19670790104.
  5. ↑ Clark, R. J.; Busch, M. A. (1973). "Stereochemical Studies of Metal Carbonyl-Phosphorus Trifluoride Complexes". Accounts of Chemical Research. 6 (7): 246–252. doi:10.1021/ar50067a005.
  6. ↑ Williams, A. A.; Parry, R. W.; Dess, H. (1957). "Phosphorus(III) Fluoride". Inorganic Syntheses. Inorganic Syntheses. Vol. 5. pp. 95–97. doi:10.1002/9780470132364.ch26. ISBN   978-0-470-13164-0.
  7. ↑ Dubrisay, R. (1956). Pascal, P. (ed.). Azote-Phosphore. Nouveau Traité de Chimie Minérale. Vol. 10. Paris, France: Masson. ISBN   978-2-225-57123-7.
  8. ↑ Clark, R. J.; Belefant, H.; Williamson, S. M. (1990). Phosphorus Trifluoride. Inorganic Syntheses. Vol. 28. pp. 310–315. doi:10.1002/9780470132593.ch77. ISBN   978-0-470-13259-3.
  9. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.

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