Thiophosphoryl fluoride

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Thiophosphoryl fluoride
Thiophosphoryl fluoride.svg
Thiophosphoryl fluoride molecule spacefill.png
Names
IUPAC name
Trifluoro(sulfanylidene)-λ5-phosphane
Other names
  • Phosphorothioc trifluoride [1]
  • Phosphorothioic trifluoride
  • Phosphorus fluoride sulfide
  • Phosphorus sulfurtrifluoride
  • Phosphorus thiofluoride
  • Thiophosphoryl trifluoride
  • Trifluorophosphine sulfide
  • Trifluoro-λ5-phosphanethione [2]
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/F3PS/c1-4(2,3)5 X mark.svgN
    Key: LHGOOQAICOQNRG-UHFFFAOYSA-N X mark.svgN
  • [3] :FP(F)(F)=S
Properties
PSF3
Molar mass 120.035 g/mol
AppearanceColorless gas or liquid
Density 1.56g/cm3 liquid [4] 4.906 g/L as gas [1]
Melting point −148.8 °C (−235.8 °F; 124.3 K)
Boiling point −52.25 °C (−62.05 °F; 220.90 K)
slight, Highly reactive
Structure
Tetrahedral at the P atom
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Spontaneously flammable in air; toxic fumes
Flash point very low
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Thiophosphoryl fluoride is an inorganic molecular gas with formula P S F 3 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, [5] and called it "probably one of the coldest flames known". [5] The gas was discovered in 1888. [5]

Contents

It is useless for chemical warfare as it burns immediately and is not toxic enough. [6]

Preparation

Thiophosphoryl fluoride was discovered and named by J. W. Rodger and T. E. Thorpe in 1888. [5] [7]

They prepared it by heating arsenic trifluoride and thiophosphoryl chloride together in a sealed glass tube to 150 °C. Also produced in this reaction was silicon tetrafluoride and phosphorus fluorides. By increasing the PSCl3 the proportion of PSF3 was increased. They observed the spontaneous inflammability. They also used this method:

3 PbF2 + P2S5 → 3 PbS + PSF3

at 170 °C, and also substituting a mixture of red phosphorus and sulfur, and substituting bismuth trifluoride. [5]

Another way to prepare PSF3 is to add fluoride to PSCl3 using sodium fluoride in acetonitrile. [8]

A high yield reaction can be used to produce the gas: [9] [ citation needed ]

P4S10 + 12 HF → 6 H2S + 4 PSF3

Under high pressure phosphorus trifluoride can react with hydrogen sulfide to yield: [10]

PF3 + H2S → PSF3 + H2 (1350 bar at 200 °C)

Another high pressure production uses phosphorus trifluoride with sulfur. [10]

Reactions

PSF3 is decomposed by moisture and oxygen or heat. With heat, phosphorus, sulfur and phosphorus fluorides are formed:

PSF3 → PF3 + S

The hot gas reacts with glass producing SF4, sulfur and elemental phosphorus. The pure gas is completely absorbed by alkali solutions. However, it does not react with ether, benzene, carbon disulfide, or pure sulfuric acid. It is stable against CaO, which can be used to remove impurities such as SiF4 and PF3. In air it burns spontaneously with a greyish green flame, producing solid white fumes. With dry oxygen combustion may not be spontaneous and the flame is yellow. On burning SO2 and P2O5 are produced. The gas burns with one of the coldest flames known. [5]

Reaction with water is slow:

PSF3 + 4 H2O → H2S + H3PO4 + 3 HF

If PSF3 is allowed to react with water in a lead glass container, the hydrofluoric acid and hydrogen sulfide combination produces a black deposit of lead sulfide on the inner surface of the glass. [5]

It reacts with four times its volume of ammonia gas producing ammonium fluoride and a mystery product, possibly P(NH2)2SF. [5]

PSF3 is an initiator for the polymerization of tetrahydrofuran. [11]

Sulfur removal

2 PSF3 + SO2 → 2 POF3 + 3 S

This reaction indicates why PSF3 is not formed from PF3 and SO2. [10]

PSF3 + SO3 → POF3 + 2 S and sulfur and sulfur sesquioxide (S2+4 polysulfate) as additional products. [12] [ clarification needed ]

Fluorine substitution

PSF3 + 2 ICl → PCl2F3. [13] [ clarification needed ]
PSF3 combines with dimethylamine in solution to produce dimethylaminothiophosphoryl difluoride (H3C−)2N−P(=S)F2 and difluorophosphate and hexafluorophosphate ions. [14]

Thiophosphoryl difluoride isocyanate can be formed by reacting PSF3 with silicontetraisocyanate at 200 °C in an autoclave. [9]

Cations

PSF3 reacts with alkali solutions producing the fluoride and a thiophosphate (PSO3−3). [5]

CsF + 2 PSF3 → Cs[PF6] + CsPS2F2 [15]

The reaction is showing the PSF3 gas is related to the difluorodithiophosphate cation PS2F−2. [16]

The CsPS2F2 is caesium difluorodithiophosphate.

PSF3 reacts with [SF6]− in a mass spectrometer to form [PSF4]−. [17]

PSF3 + [SF6]− → [PSF4]− + SF5•

One fluorine can be substituted by iodine to give thiophosphoryl difluoride iodide, PSIF2. [18] PSIF2 can be converted to hydrothiophosphoryldifluoride, S=PHF2, by reducing it with hydrogen iodide. [19] In F2P(=S)−S−PF2, one sulfur forms a bridge between two phosphorus atoms. [18]

Dimethylaminothiophosphoryl difluoride ((H3C−)2N−P(=S)F2) is a foul smelling liquid with a boiling point of 117 °C. It has a Trouton constant (entropy of vaporization at the boiling point of the liquid) of 24.4, and a heat of evaporation of 9530 cal/mole. Alternately it can be produced by fluorination of dimethylaminothiophosphoryl dichloride ((H3C−)2N−P(=S)Cl2).

Physical properties

The thiophosphoryl trifluoride molecule shape has been determined using electron diffraction. The interatomic distances are P=S 0.187±0.003 nm, P−F 0.153±0.002 nm and bond angles of F−P−F bonding is 100.3±2°, The microwave rotational spectrum has been measured for several different isotopologues. [20]

The critical point is at 346 K at 3.82 MPa. [21] The liquid refractive index is 1.353. [4]

The enthalpy of vaporisation 19.6 kJ/mol at boiling point. [22] The enthalpy of vaporisation at other temperatures is a function of temperature T: H(T)=28.85011(346-T)0.38 kJ/mol. [23]

The molecule is polar. It has a non-uniform distribution of positive and negative charge which gives it a dipole moment. When an electric field is applied more energy is stored than if the molecules did not respond by rotating. This increases the dielectric constant. The dipole moment of one molecule of thiophosphoryl trifluoride is 0.640 Debye. [24]

The infrared spectrum includes vibrations at 275, 404, 442, 698, 951 and 983 cm−1. [25] These can be used to identify the molecule.

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:

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

Sulfur tetrafluoride is the chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous HF upon exposure to water or moisture. Despite these unwelcome characteristics, this compound 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">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">Diethylaminosulfur trifluoride</span> Chemical compound

Diethylaminosulfur trifluoride (DAST) is the organosulfur compound with the formula Et2NSF3. This liquid is a fluorinating reagent used for the synthesis of organofluorine compounds. The compound is colourless; older samples assume an orange colour.

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

The tetrafluoroammonium cation is a positively charged polyatomic ion with chemical formula NF+
4. It is equivalent to the ammonium ion where the hydrogen atoms surrounding the central nitrogen atom have been replaced by fluorine. Tetrafluoroammonium ion is isoelectronic with tetrafluoromethane CF
4, trifluoramine oxide ONF
3 and the tetrafluoroborate BF−
4 anion.

<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.

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

Sulfur chloride pentafluoride is an inorganic compound with the formula SF5Cl. It exists as a colorless gas at room temperature and is highly toxic, like most inorganic compounds containing the pentafluorosulfide functional group. The compound adopts an octahedral geometry with C
4v symmetry. Sulfur chloride pentafluoride is the only commercially available reagent for adding the –SF5 group to organic compounds.

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

Vanadium(V) fluoride is the inorganic compound with the chemical formula VF5. It is a colorless volatile liquid that freezes near room temperature. It is a highly reactive compound, as indicated by its ability to fluorinate organic substances.

Phosphoryl fluoride is a compound with the chemical formula POF3. It is a colorless gas that hydrolyzes rapidly. It has a critical temperature of 73 °C and a critical pressure of 4.25 bars.

Chromium pentafluoride is the inorganic compound with the chemical formula CrF5. It is a red volatile solid that melts at 34 °C. It is the highest known chromium fluoride, since the hypothetical chromium hexafluoride has not yet been synthesized.

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">Platinum tetrafluoride</span> Chemical compound

Platinum tetrafluoride is the inorganic compound with the chemical formula PtF
4. In the solid state, the compound features platinum(IV) in octahedral coordination geometry.

<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.

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.

<span class="mw-page-title-main">Terbium(IV) fluoride</span> Chemical compound

Terbium(IV) fluoride is an inorganic compound with a chemical formula TbF4. It is a white solid that is a strong oxidizer. It is also a strong fluorinating agent, emitting relatively pure atomic fluorine when heated, rather than the mixture of fluoride vapors emitted from cobalt(III) fluoride or cerium(IV) fluoride. It can be produced by the reaction between very pure terbium(III) fluoride and xenon difluoride, chlorine trifluoride or fluorine gas:

References

  1. 1 2 A likely spelling mistake in Handbook of Chemistry and Physics 87 ed
  2. ↑ "FP(F)(F)=S".
  3. 1 2 "phosphorothioic trifluoride".
  4. 1 2 "Phosphorothioic trifluoride-(2404-52-6)-Chemical Dictionary-hgspace.com". Archived from the original on 2016-03-03. Retrieved 2012-01-29.
  5. 1 2 3 4 5 6 7 8 9 Thorpe, T. E.; Rodger, J. W. (1889). "XXXIV.?On thiophosphoryl fluoride". Journal of the Chemical Society, Transactions. 55: 306–323. doi:10.1039/CT8895500306.
  6. ↑ Banks, Ronald Eric (2000). Fluorine chemistry at the millennium: fascinated by fluorine. Elsevier. p. 502. ISBN   0-08-043405-3.
  7. ↑ Thorpe, T. E.; Rodger, J. W. (1888). "LX.?Thiophosphoryl fluoride". Journal of the Chemical Society, Transactions. 53: 766–767. doi:10.1039/CT8885300766.
  8. ↑ Padma, D. K.; Vijayalakshmi, S. K.; Vasudevamurthy, A. R. (1976). "Investigations on the preparation, oxidation and reduction reactions of thiophosphoryl fluoride". Journal of Fluorine Chemistry. 8 (6): 461. doi:10.1016/S0022-1139(00)81660-7.
  9. 1 2 Roesky, H.W. (1970). "Thiophosphoryl-difluoride-isocyanate". Journal of Inorganic and Nuclear Chemistry. 32 (6): 1845–1846. doi:10.1016/0022-1902(70)80591-7.
  10. 1 2 3 Hagen, Arnulf P.; Callaway, Bill W. (1978). "High-pressure reactions of small covalent molecules. 10. The reaction of phosphorus trifluoride with hydrogen sulfide and sulfur dioxide". Inorganic Chemistry. 17 (3): 554. doi:10.1021/ic50181a007.
  11. ↑ Padma, D.K.; Vijayalakshmi, S.K. (1978). "Thiophosphoryl fluoride and phosphoryl fluoride as initiators for the polymerisation of tetrahydrofuran". Journal of Fluorine Chemistry. 11: 51–56. doi:10.1016/S0022-1139(00)81597-3.
  12. ↑ Sampath Kumar, H.P.; Padma, D.K.; Vasudeva Murthy, A.R. (1984). "Reaction of thiophosphoryl fluoride with sulphur trioxide". Journal of Fluorine Chemistry. 26: 117–123. doi:10.1016/S0022-1139(00)85125-8.
  13. ↑ Sampath Kumar, H.P.; Padma, D.K. (1990). "Reaction of phosphorus trifluoride and thiophosphoryl fluoride with iodine monochloride and oxidation of phosphorus trifluoride with nitryl chloride, iodic acid, periodic acid, sodium nitrite and potassium nitrite". Journal of Fluorine Chemistry. 49 (3): 301. doi:10.1016/S0022-1139(00)85026-5.
  14. ↑ Cavell, R. G. (1968). "Chemistry of phosphorus fluorides. Part III. The reaction of thiophosphoryl-fluoride with dimethylamine and some properties of the dimethylaminothio- phosphoryl fluorides". Canadian Journal of Chemistry. 46 (4): 613–621. doi: 10.1139/v68-100 .
  15. ↑ Roesky, Herbert W.; Tebbe, Fred N.; Muetterties, Earl L. (1970). "Thiophosphate chemistry. Anion set X2PS2−, (XPS2)2S2−, and (XPS2)2S22−". Inorganic Chemistry. 9 (4): 831. doi:10.1021/ic50086a028.
  16. ↑ Islam, Mohammad Q.; Hill, William E.; Webb, Thomas R. (1990). "Quadruply bonded dimolybdenum complexes of PF2S2−. Comparison with complexes of PR2S2p− (R = Et, Me)". Journal of Fluorine Chemistry. 48 (3): 429. doi:10.1016/S0022-1139(00)80227-4.
  17. ↑ Rhyne, T; Dillard, J (1971). "Reactions of gaseous inorganic negative ions: III. SF6− with POF3 and PSF3". International Journal of Mass Spectrometry and Ion Physics. 7 (5): 371. Bibcode:1971IJMSI...7..371R. doi:10.1016/0020-7381(71)85003-9.
  18. 1 2 Charlton, Thomas L.; Cavell, Ronald G. (1969). "Difluorothiophosphoryl-μ-thio-difluorophosphine and difluorophosphoryl-μ-oxo-difluorophosphine. Novel mixed-valence fluorophosphorus compounds". Inorganic Chemistry. 8 (11): 2436. doi:10.1021/ic50081a037.
  19. ↑ Charlton, Thomas L.; Cavell, R. G. (1968). "Preparation and properties of iodothiophosphoryl difluoride, SPF2I". Inorganic Chemistry. 7 (11): 2195. doi:10.1021/ic50069a005.
  20. ↑ Williams, Quitman; Sheridan, John; Gordy, Walter (1952). "Microwave Spectra and Molecular Structures of POF3, PSF3, POCl3, and PSCl3". The Journal of Chemical Physics. 20 (1): 164–167. Bibcode:1952JChPh..20..164W. doi:10.1063/1.1700162.
  21. ↑ Handbook of Chemistry and Physics 87 ed page 6-39
  22. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 550. ISBN   978-0-8155-1495-4.
  23. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 406. ISBN   978-0-8155-1495-4.
  24. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 685. ISBN   978-0-8155-1495-4.
  25. ↑ Cavell, R (1967). "The infrared spectrum of thiophosphoryl fluoride". Spectrochimica Acta Part A: Molecular Spectroscopy. 23 (2): 249–256. Bibcode:1967AcSpA..23..249C. doi:10.1016/0584-8539(67)80227-7.

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