Phosphorus trifluoride

"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^Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:30205^Y
ChemSpider	56416^Y
ECHA InfoCard	100.029.098
PubChem CID	62665
RTECS number	TH3850000
UNII	496073DYBF^Y
CompTox Dashboard (EPA)	DTXSID6064826
InChI InChI=1S/F3P/c1-4(2)3^Y Key: WKFBZNUBXWCCHG-UHFFFAOYSA-N^Y 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)
Solubility in water	slow hydrolysis
Structure
Molecular shape	Trigonal pyramidal
Dipole moment	1.03 D
Hazards
NFPA 704 (fire diamond)	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). Y verify (what is ^YN ?) Infobox references

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

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]

References

1. Chatt, J. (1950). "The Co-Ordinate Link in Chemistry". Nature. 165 (4199): 637–638. 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. 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. 5: 95–97. doi:10.1002/9780470132364.ch26.
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. 28: 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.

Further reading

• 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.

External links

• WebBook page for PF3