Phosphorus trifluoride

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"F3P" redirects here. For the camera, see Nikon F3P.

Phosphorus trifluoride (formula PF3), 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.

Phosphorus trifluoride
Structure and dimensions of phosphorus trifluoride
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

CAS Number

  • 7783-55-3 check

3D model (JSmol)

  • Interactive image
ChEBI
  • CHEBI:30205 check
ChemSpider
  • 56416 check
ECHA InfoCard 100.029.098

PubChem CID

  • 62665
RTECS number
  • TH3850000
UNII
  • 496073DYBF check

CompTox Dashboard (EPA)

  • DTXSID6064826

InChI

  • InChI=1S/F3P/c1-4(2)3 check

    Key: WKFBZNUBXWCCHG-UHFFFAOYSA-N check

  • InChI=1/F3P/c1-4(2)3

    Key: WKFBZNUBXWCCHG-UHFFFAOYAK

SMILES

  • FP(F)F

Properties

Chemical formula

PF3
Molar mass 87.968971 g/mol
Appearance colorless 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)
Critical point (T, P) −2.05 °C (28.3 °F; 271.1 K); 42.73 standard atmospheres (4,329.6 kPa; 628.0 psi)

Solubility in water

slow hydrolysis
Structure

Molecular shape

Trigonal pyramidal

Dipole moment

1.03 D
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 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

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).

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Infobox references

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).

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

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

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.

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

  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.
  • Toy, A. D. F. (1973). The Chemistry of Phosphorus. Oxford, UK: Pergamon Press.
  • Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  • Lide, D. R., ed. (1990). Handbook of Chemistry and Physics (71st ed.). Ann Arbor, MI: CRC Press. ISBN 978-0-8493-0471-2.
  • March, J. (1992). Advanced Organic Chemistry (4th ed.). New York: Wiley. p. 723. ISBN 978-0-471-60180-7.
  • Stecher, P. G., ed. (1960). The Merck Index (7th ed.). Rahway, NJ, USA: Merck & Co.
  • Holmes, R. R. (1960). "An Examination of the Basic Nature of the Trihalides of Phosphorus, Arsenic and Antimony". Journal of Inorganic and Nuclear Chemistry. 12 (3–4): 266–275. doi:10.1016/0022-1902(60)80372-7.
  • National Pollutant Inventory - Fluoride and compounds fact sheet
  • WebBook page for PF3