Diphosphorus tetrafluoride

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Diphosphorus tetrafluoride
Phosphor(II)-fluorid.png
P2F4-mol-3d.png
Names
IUPAC name
difluorophosphanyl(difluoro)phosphane
Other names
tetrafluorodiphosphine; phosphorus difluoride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/F4P2/c1-5(2)6(3)4
    Key: PCIAPVMJDQUHAP-UHFFFAOYSA-N
  • FP(F)P(F)F
Properties
F4P2
Molar mass 137.941136648 g·mol−1
Melting point −86.5 °C (−123.7 °F; 186.7 K)
Boiling point −6.2 °C (20.8 °F; 266.9 K)
Related compounds
Other anions
Diphosphorus tetrachloride
Diphosphorus tetrabromide
Diphosphorus tetraiodide
Other cations
dinitrogen tetrafluoride
diarsenic tetrafluoride
Related Binary Phosphorus halides
phosphorus trifluoride
phosphorus pentafluoride
Related compounds
diphosphane
diphosphines
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Diphosphorus tetrafluoride is a gaseous compound of phosphorus and fluorine with formula P2F4. Two fluorine atoms are connected to each phosphorus atom, and there is a bond between the two phosphorus atoms. Phosphorus can be considered to have oxidation state +2, as indicated by the name phosphorus difluoride. [1]

Contents

Production

Diphosphorus tetrafluoride was discovered in 1966 by Max Lustig, John K. Ruff and Charles B. Colburn at the Redstone Research Laboratories. The initial synthesis reacted phosphorus iododifluoride with mercury at room temperature. [2]

2PF2I +2Hg → P2F4 + Hg2I2

Properties

The P-P bond in diphosphorus tetrafluoride is much stronger than the corresponding N-N bond in dinitrogen tetrafluoride which easily breaks into nitrogen difluoride. [2]

The infrared spectrum has absorption at 842 cm−1, 830 cm−1, 820 cm−1, and weaker at 408 cm−1 and 356 cm−1. [2]

The molecule has C2h symmetry. [3]

Reactions

Under ultraviolet light diphosphorus tetrafluoride reacts with alkynes connected to trifluoromethyl groups to add difluorophosphino (-PF2) groups on each side of a double bond. Other kinds of alkynes produced polymers with this treatment. [4] With alkenes, similarly bis(difluorophosphino) is added across the double bond. [5]

Diphosphorus tetrafluoride reacts with diborane to yield another gas P2F4•BH3 which does not condense above −85°C. This decomposes to yet another gas PF3•BH3 and a polymer with formula PF. [6]

Diphosphorus tetrafluoride reacts with oxygen or water to yield diphosphorus tetrafluoride oxide, which has one oxygen atom inserted between the two phosphorus atoms: [2] [7]

The latter compound is a gas with boiling point around −18°C.

Related Research Articles

In chemistry, a hypervalent molecule is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Phosphorus pentachloride, sulfur hexafluoride, chlorine trifluoride, the chlorite ion, and the triiodide ion are examples of hypervalent molecules.

<span class="mw-page-title-main">Oxygen fluoride</span> Any binary compound of oxygen and fluorine

Oxygen fluorides are compounds of elements oxygen and fluorine with the general formula OnF2, where n = 1 to 6. Many different oxygen fluorides are known:

<span class="mw-page-title-main">Trigonal bipyramidal molecular geometry</span> Molecular structure with atoms at the center and vertices of a triangular bipyramid

In chemistry, a trigonal bipyramid formation is a molecular geometry with one atom at the center and 5 more atoms at the corners of a triangular bipyramid. This is one geometry for which the bond angles surrounding the central atom are not identical, because there is no geometrical arrangement with five terminal atoms in equivalent positions. Examples of this molecular geometry are phosphorus pentafluoride, and phosphorus pentachloride in the gas phase.

Dioxygen difluoride is a compound of fluorine and oxygen with the molecular formula O2F2. It can exist as an orange-colored solid which melts into a red liquid at −163 °C (110 K). It is an extremely strong oxidant and decomposes into oxygen and fluorine even at −160 °C (113 K) at a rate of 4% per dayits lifetime at room temperature is thus extremely short. Dioxygen difluoride reacts vigorously with nearly every chemical it encounters (including ordinary ice) leading to its onomatopoeic nickname "FOOF" (a play on its chemical structure and its explosive tendencies).

<span class="mw-page-title-main">Xenon difluoride</span> Chemical compound

Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2
, and one of the most stable xenon compounds. Like most covalent inorganic fluorides it is moisture-sensitive. It decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.

<span class="mw-page-title-main">Selenium tetrafluoride</span> Chemical compound

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

<span class="mw-page-title-main">Krypton difluoride</span> Chemical compound

Krypton difluoride, KrF2 is a chemical compound of krypton and fluorine. It was the first compound of krypton discovered. It is a volatile, colourless solid. The structure of the KrF2 molecule is linear, with Kr−F distances of 188.9 pm. It reacts with strong Lewis acids to form salts of the KrF+ and Kr
2
F+
3
cations.

<span class="mw-page-title-main">Dioxygenyl</span> Chemical compound

The dioxygenyl ion, O+
2
, is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of +1/2. It is formally derived from oxygen by the removal of an electron:

<span class="mw-page-title-main">Thionyl tetrafluoride</span> Chemical compound

Thionyl tetrafluoride is an inorganic compound gas with the formula SOF4. It is also known as sulfur tetrafluoride oxide. The shape of the molecule is a distorted trigonal bipyramid, with the oxygen found on the equator. The atoms on the equator have shorter bond lengths than the fluorine atoms on the axis. The sulfur oxygen bond is 1.409Å. A S−F bond on the axis has length 1.596Å and the S−F bond on the equator has length 1.539Å. The angle between the equatorial fluorine atoms is 112.8°. The angle between axial fluorine and oxygen is 97.7°. The angle between oxygen and equatorial fluorine is 123.6° and between axial and equatorial fluorine is 85.7°. The fluorine atoms only produce one NMR line, probably because they exchange positions.

Boron monofluoride or fluoroborylene is a chemical compound with formula BF, one atom of boron and one of fluorine. It was discovered as an unstable gas and only in 2009 found to be a stable ligand combining with transition metals, in the same way as carbon monoxide. It is a subhalide, containing fewer than the normal number of fluorine atoms, compared with boron trifluoride. It can also be called a borylene, as it contains boron with two unshared electrons. BF is isoelectronic with carbon monoxide and dinitrogen; each molecule has 14 electrons.

<span class="mw-page-title-main">Thiophosphoryl fluoride</span> Chemical compound

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

<span class="mw-page-title-main">Fluorine azide</span> Chemical compound

Fluorine azide or triazadienyl fluoride is a yellow green gas composed of nitrogen and fluorine with formula FN3. It is counted as an interhalogen compound, as the azide functional group is termed a pseudohalogen. It resembles ClN3, BrN3, and IN3 in this respect. The bond between the fluorine atom and the nitrogen is very weak, leading to this substance being very unstable and prone to explosion. Calculations show the F–N–N angle to be around 102° with a straight line of 3 nitrogen atoms.

Chlorotrifluorosilane is an inorganic gaseous compound with formula SiClF3 composed of silicon, fluorine and chlorine. It is a silane that substitutes hydrogen with fluorine and chlorine atoms.

<span class="mw-page-title-main">Difluorophosphate</span> Chemical compound

Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula PO
2
F
2
. It has a single negative charge and resembles perchlorate (ClO
4
) and monofluorosulfonate (SO3F) in shape and compounds. These ions are isoelectronic, along with tetrafluoroaluminate, phosphate, orthosilicate, and sulfate. It forms a series of compounds. The ion is toxic to mammals as it causes blockage to iodine uptake in the thyroid. However it is degraded in the body over several hours.

<span class="mw-page-title-main">Nitrogen difluoride</span> Chemical compound

Nitrogen difluoride, also known as difluoroamino, is a reactive radical molecule with formula NF2. This small molecule is in equilibrium with its dimer dinitrogen tetrafluoride.

Difluoroamino sulfur pentafluoride is a gaseous chemical compound of fluorine, sulfur, and nitrogen. It is unusual in having a hexa-coordinated sulfur atom with a link to nitrogen. Other names for this substance include difluoro(pentafluorosulfur)amine, pentafluorosulfanyldifluoramine, and pentafluorosulfanyl N,N-difluoramine.

<span class="mw-page-title-main">Difluorodisulfanedifluoride</span> Chemical compound

1,1,1,2-tetrafluorodisulfane, also known as 1,2-difluorodisulfane 1,1-difluoride or just difluorodisulfanedifluoride (FSSF3) is an unstable molecular compound of fluorine and sulfur. The molecule has a pair of sulfur atoms, with one fluorine atom on one sulfur, and three fluorine atoms on the other. It has the uncommon property that all the bond lengths are different. The bond strength is not correlated with bond length but is inversely correlated with the force constant (Badger's rule). The molecule can be considered as sulfur tetrafluoride in which a sulfur atom is inserted into a S-F bond.

Pentafluorosulfur hypofluorite is an oxyfluoride of sulfur in the +6 oxidation state, with a fluorine atom attached to oxygen. The formula is SOF6. In standard conditions it is a gas.

Karen Dale Williams Morse is a inorganic chemist. She was president of Western Washington University from 1993 until 2008, and was named the Bowman Distinguished Professor in 2014. She is an elected fellow of the American Association for the Advancement of Science.

References

  1. Toy, Arthur D. F. (2016). The Chemistry of Phosphorus: Pergamon Texts in Inorganic Chemistry. Elsevier. p. 418. ISBN   978-1-4831-3959-3.
  2. 1 2 3 4 Lustig, Max; Ruff, John K.; Colburn, Charles B. (August 1966). "Diphosphorus Tetrafluoride and Diphosphorus Oxytetrafluoride". Journal of the American Chemical Society. 88 (16): 3875. doi:10.1021/ja00968a046.
  3. Rhee, Kee H.; Snider, A.Monroe; Miller, Foil A. (June 1973). "Infrared and Raman spectra and structure of P2F4". Spectrochimica Acta Part A: Molecular Spectroscopy. 29 (6): 1029–1035. Bibcode:1973AcSpA..29.1029R. doi:10.1016/0584-8539(73)80142-4.
  4. Morse, J.G.; Mielcarek, J.J. (July 1988). "Photoreactions of tetrafluorodiphosphine with alkynes". Journal of Fluorine Chemistry. 40 (1): 41–49. doi:10.1016/S0022-1139(00)81060-X.
  5. Morse, Joseph G.; Morse, Karen W. (March 1975). "Photoreactions of tetrafluorodiphosphine with nonsubstituted olefins and perfluoroolefins". Inorganic Chemistry. 14 (3): 565–569. doi:10.1021/ic50145a024.
  6. Morse, Karen W.; Parry, Robert W. (January 1967). "The Basic Properties of Tetrafluorodiphosphine. The Synthesis of Tetrafluorodiphosphine Borane". Journal of the American Chemical Society. 89 (1): 172–173. doi:10.1021/ja00977a049.
  7. Rudolph, R. W.; Taylor, R. C.; Parry, R. W. (August 1966). "Fluorophosphine Ligands. III. Syntheses Involving PF I. The Preparation and Characterization of μ-Oxo-bisdifluorophosphine, Cyanodifluorophosphine, and Tetrafluorodiphosphine". Journal of the American Chemical Society. 88 (16): 3729–3734. doi:10.1021/ja00968a010. PMID   5916370.