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Phosphorus pentafluoride

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Phosphorus pentafluoride
Structure of the phosphorus pentafluoride molecule
Space-filling model of the phosphorus pentafluoride molecule
Names
IUPAC name Phosphorus pentafluoride
Other names Phosphorus(V) fluoride
Pentafluoridophosphorus
Pentafluorophosphorane
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.730 Edit this at Wikidata
EC Number
  • 231-602-3
PubChem CID
RTECS number
  • TH4070000
UNII
UN number 2198
CompTox Dashboard (EPA)
InChI
  • InChI=1S/F5P/c1-6(2,3,4)5Key: OBCUTHMOOONNBS-UHFFFAOYSA-N
  • InChI=1/F5P/c1-6(2,3,4)5Key: OBCUTHMOOONNBS-UHFFFAOYAH
SMILES
  • FP(F)(F)(F)F
Properties
Chemical formula PF5
Molar mass 125.965777813 g·mol
Appearance colourless gas
Odor unpleasant
Density 5.527 kg/m
Melting point −93.78 °C (−136.80 °F; 179.37 K)
Boiling point −84.6 °C (−120.3 °F; 188.6 K)
Critical point (T, P) 19 °C (66.2 °F; 292.1 K), 33.9 standard atmospheres (3,430 kPa; 498 psi)
Solubility in water hydrolysis
Structure
Molecular shape trigonal bipyramidal
Dipole moment 0 D
Hazards
Flash point Non-flammable
Related compounds
Other anions Phosphorus pentachloride
Phosphorus pentabromide
Phosphorus pentaiodide
Other cations Arsenic pentafluoride
Antimony pentafluoride
Bismuth pentafluoride
Related compounds Phosphorus trifluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

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

Preparation

Phosphorus pentafluoride was first prepared in 1876 by the fluorination of phosphorus pentachloride using arsenic trifluoride, which remains a favored method:

3 PCl5 + 5 AsF3 → 3 PF5 + 5 AsCl3

Phosphorus pentafluoride can be prepared by direct combination of phosphorus and fluorine:

P4 + 10 F2 → 4 PF5

Structure

Single-crystal X-ray studies indicate that the PF5 has trigonal bipyramidal geometry. Thus it has two distinct types of P−F bonds (axial and equatorial): the length of an axial P−F bond is distinct from the equatorial P−F bond in the solid phase, but not the liquid or gas phases due to Berry pseudo rotation.

Fluorine-19 NMR spectroscopy, even at temperatures as low as −100 °C, fails to distinguish the axial from the equatorial fluorine environments. The apparent equivalency arises from the low barrier for pseudorotation via the Berry mechanism, by which the axial and equatorial fluorine atoms rapidly exchange positions. The apparent equivalency of the F centers in PF5 was first noted by Gutowsky. The explanation was first described by R. Stephen Berry, after whom the Berry mechanism is named. Berry pseudorotation influences the F NMR spectrum of PF5 since NMR spectroscopy operates on a millisecond timescale. Electron diffraction and X-ray crystallography do not detect this effect as the solid state structures are, relative to a molecule in solution, static and can not undergo the necessary changes in atomic position.

Lewis acidity

Phosphorus pentafluoride is a Lewis acid. This property is relevant to its ready hydrolysis. A well studied adduct is PF5 with pyridine. With primary and secondary amines, the adducts convert readily to dimeric amido-bridged derivatives with the formula 2. A variety of complexes are known with bidentate ligands.

Hexafluorophosphoric acid (HPF6) is derived from phosphorus pentafluoride and hydrogen fluoride. Its conjugate base, hexafluorophosphate (PF6), is a useful non-coordinating anion. It is often used in lithium-ion batteries, where besides providing good ionic conductivity for the liquid electrolyte, it also passivates positive aluminium current collector.

References

  1. ^ Kwasnik, W. (1963). "Phosphorus(V) fluoride". In Brauer, G. (ed.). Handbook of Preparative Inorganic Chemistry. Vol. 1 (2nd ed.). New York: Academic Press. p. 190.
  2. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  3. Gutowsky, H. S.; McCall, D. W.; Slichter, C. P. (1953). "Nuclear Magnetic Resonance Multiplets in Liquids". J. Chem. Phys. 21 (2): 279. doi:10.1063/1.1698874.
  4. Wong, Chih Y.; Kennepohl, Dietmar K.; Cavell, Ronald G. (1996). "Neutral Six-Coordinate Phosphorus". Chemical Reviews. 96 (6): 1917–1952. doi:10.1021/cr9410880. PMID 11848816.
Phosphorus compounds
Phosphides
Other compounds
Fluorine compounds
Salts and covalent derivatives of the fluoride ion
HF ?HeF2
LiF BeF2 BF
BF3
B2F4
+BO3
CF4
CxFy
+CO3
NF3
FN3
N2F2
NF
N2F4
NF2
?NF5
OF2
O2F2
OF
O3F2
O4F2
?OF4
F2 Ne
NaF MgF2 AlF
AlF3
SiF4 P2F4
PF3
PF5
S2F2
SF2
S2F4
SF3
SF4
S2F10
SF6
+SO4
ClF
ClF3
ClF5
?ArF2
?ArF4
KF CaF
CaF2
ScF3 TiF2
TiF3
TiF4
VF2
VF3
VF4
VF5
CrF2
CrF3
CrF4
CrF5
?CrF6
MnF2
MnF3
MnF4
?MnF5
FeF2
FeF3
FeF4
CoF2
CoF3
CoF4
NiF2
NiF3
NiF4
CuF
CuF2
?CuF3
ZnF2 GaF2
GaF3
GeF2
GeF4
AsF3
AsF5
Se2F2
SeF4
SeF6
+SeO3
BrF
BrF3
BrF5
KrF2
?KrF4
?KrF6
RbF SrF
SrF2
YF3 ZrF2
ZrF3
ZrF4
NbF4
NbF5
MoF4
MoF5
MoF6
TcF4
TcF
5

TcF6
RuF3
RuF
4

RuF5
RuF6
RhF3
RhF4
RhF5
RhF6
PdF2
Pd
PdF4
?PdF6
Ag2F
AgF
AgF2
AgF3
CdF2 InF
InF3
SnF2
SnF4
SbF3
SbF5
TeF4
?Te2F10
TeF6
+TeO3
IF
IF3
IF5
IF7
+IO3
XeF2
XeF4
XeF6
?XeF8
CsF BaF2   LuF3 HfF4 TaF5 WF4
WF5
WF6
ReF4
ReF5
ReF6
ReF7
OsF4
OsF5
OsF6
?OsF
7

?OsF
8
IrF2
IrF3
IrF4
IrF5
IrF6
PtF2
Pt
PtF4
PtF5
PtF6
AuF
AuF3
Au2F10
?AuF6
AuF5•F2
Hg2F2
HgF2
?HgF4
TlF
TlF3
PbF2
PbF4
BiF3
BiF5
?PoF2
PoF4
PoF6
AtF
?AtF3
?AtF5
RnF2
?RnF
4

?RnF
6
FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
LaF3 CeF3
CeF4
PrF3
PrF4
NdF2
NdF3
NdF4
PmF3 SmF2
SmF3
EuF2
EuF3
GdF3 TbF3
TbF4
DyF2
DyF3
DyF4
HoF3 ErF3 TmF2
TmF3
YbF2
YbF3
AcF3 ThF3
ThF4
PaF4
PaF5
UF3
UF4
UF5
UF6
NpF3
NpF4
NpF5
NpF6
PuF3
PuF4
PuF5
PuF6
AmF2
AmF3
AmF4
?AmF6
CmF3
CmF4
 ?CmF6
BkF3
BkF
4
CfF3
CfF4
EsF3
EsF4
?EsF6
Fm Md No
PF−6, AsF−6, SbF−6 compounds
AlF−6 compounds
chlorides, bromides, iodides
and pseudohalogenides
SiF2−6, GeF2−6 compounds
Oxyfluorides
Organofluorides
with transition metal,
lanthanide, actinide, ammonium
nitric acids
bifluorides
thionyl, phosphoryl,
and iodosyl
Chemical formulas
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