Phosphorus trifluoride

Phosphorus trifluoride
Structure and dimensions of phosphorus trifluoride
Structure and dimensions of phosphorus trifluoride
Space-filling model 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 checkY
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:30205 checkY
ChemSpider
  • 56416 checkY
ECHA InfoCard 100.029.098 Edit this at Wikidata
PubChem CID
  • 62665
RTECS number
  • TH3850000
UNII
  • 496073DYBF checkY
CompTox Dashboard (EPA)
  • DTXSID6064826 Edit this at Wikidata
InChI
  • InChI=1S/F3P/c1-4(2)3 checkY
    Key: WKFBZNUBXWCCHG-UHFFFAOYSA-N checkY
  • InChI=1/F3P/c1-4(2)3
    Key: WKFBZNUBXWCCHG-UHFFFAOYAK
  • 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
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
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).
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Infobox references
Chemical compound

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.

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

  • National Pollutant Inventory - Fluoride and compounds fact sheet
  • WebBook page for PF3
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Phosphides
Other compounds
  • PBr3
  • PBr5
  • PBr7
  • PCl3
  • PCl5
  • P2Cl4
  • PF3
  • PF5
  • PI3
  • PH3
  • PN
  • P3N5
  • PO
  • P2O3
  • P2O4
  • P2O5
  • P4S3
  • P4Sx
  • P4S10
  • v
  • t
  • e
HF He
LiF BeF2 BF
BF3
B2F4
CF4
CxFy
NF3
N2F4
OF
OF2
O2F2
O2F
F Ne
NaF MgF2 AlF
AlF3
SiF4 P2F4
PF3
PF5
S2F2
SF2
S2F4
SF4
S2F10
SF6
ClF
ClF3
ClF5
HArF
ArF2
KF CaF2 ScF3 TiF3
TiF4
VF2
VF3
VF4
VF5
CrF2
CrF3
CrF4
CrF5
CrF6
MnF2
MnF3
MnF4
FeF2
FeF3
CoF2
CoF3
NiF2
NiF3
CuF
CuF2
ZnF2 GaF3 GeF4 AsF3
AsF5
SeF4
SeF6
BrF
BrF3
BrF5
KrF2
KrF4
KrF6
RbF SrF2 YF3 ZrF4 NbF4
NbF5
MoF4
MoF5
MoF6
TcF6 RuF3
RuF4
RuF5
RuF6
RhF3
RhF5
RhF6
PdF2
Pd[PdF6]
PdF4
PdF6
AgF
AgF2
AgF3
Ag2F
CdF2 InF3 SnF2
SnF4
SbF3
SbF5
TeF4
TeF6
IF
IF3
IF5
IF7
XeF2
XeF4
XeF6
XeF8
CsF BaF2 * LuF3 HfF4 TaF5 WF4
WF6
ReF6
ReF7
OsF4
OsF5
OsF6
OsF
7

OsF8
IrF3
IrF5
IrF6
PtF2
Pt[PtF6]
PtF4
PtF5
PtF6
AuF
AuF3
Au2F10
AuF5·F2
HgF2
Hg2F2
HgF4
TlF
TlF3
PbF2
PbF4
BiF3
BiF5
PoF4
PoF6
At RnF2
RnF6
Fr RaF2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
* LaF3 CeF3
CeF4
PrF3
PrF4
NdF3 PmF3 SmF2
SmF3
EuF2
EuF3
GdF3 TbF3
TbF4
DyF3 HoF3 ErF3 TmF2
TmF3
YbF2
YbF3
** AcF3 ThF4 PaF4
PaF5
UF3
UF4
UF5
UF6
NpF3
NpF4
NpF5
NpF6
PuF3
PuF4
PuF5
PuF6
AmF3
AmF4
AmF6
CmF3 Bk Cf Es Fm Md No
PF6, AsF6, SbF6 compounds
  • AgPF6
  • KAsF6
  • LiAsF6
  • NaAsF6
  • HPF6
  • HSbF6
  • NH4PF6
  • KPF6
  • KSbF6
  • LiPF6
  • NaPF6
  • NaSbF6
  • TlPF6
AlF6 compounds
  • Cs2AlF5
  • K3AlF6
  • Na3AlF6
chlorides, bromides, iodides
and pseudohalogenides
SiF62-, GeF62- compounds
  • BaSiF6
  • BaGeF6
  • (NH4)2SiF6
  • Na2[SiF6]
  • K2[SiF6]
Oxyfluorides
  • BrOF3
  • BrO2F
  • BrO3F
  • LaOF
  • ThOF2
  • VOF
    3
  • TcO
    3
    F
  • WOF
    4
  • YOF
  • ClOF3
  • ClO2F3
Organofluorides
  • CBrF3
  • CBr2F2
  • CBr3F
  • CClF3
  • CCl2F2
  • CCl3F
  • CF2O
  • CF3I
  • CHF3
  • CH2F2
  • CH3F
  • C2Cl3F3
  • C2H3F
  • C6H5F
  • C7H5F3
  • C15F33N
  • C3H5F
  • C6H11F
with transition metal,
lanthanide, actinide, ammonium
  • VOF3
  • CrOF4
  • CrF2O2
  • NH4F
  • (NH4)2ZrF6
  • CsXeF7
  • Li2TiF6
  • Li2ZrF6
  • K2TiF6
  • Rb2TiF6
  • Na2TiF6
  • Na2ZrF6
  • K2NbF7
  • K2TaF7
  • K2ZrF6
  • UO2F2
nitric acids
bifluorides
  • KHF2
  • NaHF2
  • NH4HF2
thionyl, phosphoryl,
and iodosyl
  • F2OS
  • F3OP
  • PSF3
  • IOF3
  • IO3F
  • IOF5
  • IO2F
  • IO2F3