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]

2 PF2I + 2 Hg → 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]

2 P2F4 + H2O → 2 PHF2 + F2POPF2

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

Related Research Articles

<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:

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.

Xenon compounds are compounds containing the element xenon (Xe). After Neil Bartlett's discovery in 1962 that xenon can form chemical compounds, a large number of xenon compounds have been discovered and described. Almost all known xenon compounds contain the electronegative atoms fluorine or oxygen. The chemistry of xenon in each oxidation state is analogous to that of the neighboring element iodine in the immediately lower oxidation state.

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

Sulfur tetrafluoride is a chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous hydrogen fluoride gas upon exposure to water or moisture. Sulfur tetrafluride is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

<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">Tetrafluorohydrazine</span> Chemical compound

Tetrafluorohydrazine or perfluorohydrazine, N2F4, is a colourless, nonflammable, reactive inorganic gas. It is a fluorinated analog of hydrazine.

<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 at room temperature. 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:

Dinitrogen difluoride is a chemical compound with the formula N2F2. It is a gas at room temperature, and was first identified in 1952 as the thermal decomposition product of the fluorine azide. It has the structure F−N=N−F and exists in both cis and trans isomers, as typical for diimides.

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

Thionyl tetrafluoride, also known as sulfur tetrafluoride oxide, is an inorganic compound with the formula SOF4. It is a colorless gas.

Boron monofluoride or fluoroborylene is a chemical compound with the formula BF, one atom of boron and one of fluorine. It is an unstable gas, but it is a stable ligand on 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.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

<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.

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 PO2F−2. It has a single negative charge and resembles perchlorate and monofluorosulfonate 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.

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.

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.