Phosphorus trifluoride (formula
P F3), is a colorless and odorless
gas
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
. It is highly toxic and reacts slowly with water. Its main use is as a
ligand in
metal complexes
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
. As a ligand, it parallels
carbon monoxide
Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...
in
metal carbonyl
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe c ...
s,
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°.
Gas
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
eous PF
3 has a
standard enthalpy of formation
In chemistry and thermodynamics, the standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements in their reference state, wi ...
of −945 kJ/mol (−226
kcal
The calorie is a unit of energy. For historical reasons, two main definitions of "calorie" are in wide use. The large calorie, food calorie, or kilogram calorie was originally defined as the amount of heat needed to raise the temperature of o ...
/
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
In chemistry, there are three definitions in common use of the word base, known as Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Ro ...
, 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
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typica ...
s, phosphides and fluorides are formed. With
Lewis bases such as
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous wa ...
addition products (adducts) are formed, and PF
3 is oxidized by
oxidizing agents such as
bromine
Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table (halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simila ...
or
potassium permanganate.
As a ligand for transition metals, PF
3 is a strong π-acceptor.
It forms a variety of
metal complexes
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
with
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typica ...
s in low
oxidation states. PF
3 forms several complexes for which the corresponding CO derivatives (see
metal carbonyl
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe c ...
) are unstable or nonexistent. Thus, Pd(PF
3)
4 is known, but Pd(CO)
4 is not.
Such complexes are usually prepared directly from the related
metal carbonyl
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe c ...
compound, with loss of
CO. However,
nickel metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typica ...
reacts directly with PF
3 at 100 °C under 35
MPa
MPA or mPa may refer to:
Academia
Academic degrees
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Schools
* Mesa Preparatory Academy
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pressure to form Ni(PF
3)
4, which is analogous to
Ni(CO)4. Cr(PF
3)
6, the analogue of
Cr(CO)6, may be prepared from
dibenzenechromium:
:
Cr(C6H6)2 + 6 PF
3 → Cr(PF
3)
6 + 2
C6H6
Preparation
Phosphorus trifluoride is usually prepared from
phosphorus trichloride via halogen exchange using various
fluoride
Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts ty ...
s such as
hydrogen fluoride,
calcium fluoride
Calcium fluoride is the inorganic compound of the elements calcium and fluorine with the formula CaF2. It is a white insoluble solid. It occurs as the mineral fluorite (also called fluorspar), which is often deeply coloured owing to impurities.
...
,
arsenic trifluoride,
antimony trifluoride
Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, i ...
, or
zinc fluoride
Zinc fluoride ( Zn F2) is an inorganic chemical compound. It is encountered as the anhydrous form and also as the tetrahydrate, ZnF2 · 4H2O (rhombohedral crystal structure). It has a high melting point and has the rutile structure containing 6 ...
:
:2
PCl3 + 3
ZnF2 → 2 PF
3 + 3
ZnCl2
Biological activity
Phosphorus trifluoride is similar to
carbon monoxide
Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...
in that it is a gas which strongly binds to
iron in
hemoglobin, preventing the blood from absorbing oxygen.
Precautions
PF
3 is highly
toxic
Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a subs ...
, comparable to
phosgene
Phosgene is the organic chemical compound with the formula COCl2. It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. Phosgene is a valued and important industrial building block, esp ...
.
References
Further reading
*
*
*
*
*
*
External links
National Pollutant Inventory - Fluoride and compounds fact sheetWebBook page for PF3
{{DEFAULTSORT:Phosphorus Trifluoride
Phosphorus fluorides
Phosphorus(III) compounds
Blood agents