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:[ citation needed ]

P4S10 + 12 HF → 6 H2S + 4 PSF3

Under high pressure phosphorus trifluoride can react with hydrogen sulfide to yield: [9]

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

Another high pressure production uses phosphorus trifluoride with sulfur. [9]

Reactions

PSF3 is unstable against moisture or heat. The pure gas is completely absorbed by alkali solutions, producing the fluoride and a thiophosphate (PSO3−3), but stable against CaO. The latter can be used to remove SiF4 or PF3 impurities. [5]

Hydrolysis and decomposition

Reaction with neutral water is slow:

PSF3 + 4 H2O → H2S + H3PO4 + 3 HF

Nevertheless, dissociation constants for related acids suggest that the phosphorus atom is at least as electrophilic as in phosphoryl fluoride. [10]

Autodecomposition from heat gives phosphorus fluorides, sulfur, and phosphorus:

PSF3 → S + PF3 → ...

Hot PSF3 reacts with glass, producing SF4, sulfur and elemental phosphorus. If water is present and the glass is leaded, then the hydrofluoric acid and hydrogen sulfide combination produces a black plumbous sulfide deposit on the inner surface. [5]

Oxidation

In air, PSF3 burns spontaneously with a greyish green flame, producing solid white fumes containing SO2 and P2O5. The flame is one of the coldest known. With dry oxygen, combustion may not be spontaneous and the flame is yellow. [5]

Thiophosphoryl fluoride reduces oxygenated compounds to give phosphoryl fluoride and sulfur: [9] [11]

PSF3 + SO3→ POF3 + SO2
2 PSF3 + SO2 → 2 POF3 + 3 S

The latter reaction also indicates why PSF3 is not formed from PF3 and SO2. [9]

Various oxidants can convert thiophosphoryl fluoride to phosphorus dichloride trifluoride, e.g.: [12]

PSF3 + 2 ICl → PCl2F3 + I2 + S.

Nucleophilic substitution

Thiophosphoryl difluoride isocyanate can be formed by reacting PSF3 with silicon tetraisocyanate at 200 °C in an autoclave. [13]

In general, nucleophilic substitution onto thiophosphoryl fluoride is complex, because free fluoride ions tend to induce disproportionation to hexafluorophosphate and dithiodifluorophosphate (PS2F−2). [10] [14] For example, with cesium fluoride: [15]

CsF + 2 PSF3 → Cs[PF6] + CsPS2F2

Thus PSF3 combines with dimethylamine in solution to produce dimethylaminothiophosphoryl difluoride (H3C−)2N−P(=S)F2 and difluorophosphate and hexafluorophosphate ions: [10] [16]

4 SPF3 + 4 HNMe2 → 2 SPF2NMe2 + [H2NMe2]PF6 + [H2NMe2]S2PF2.

PSF3 reacts with four times its volume of ammonia gas producing ammonium fluoride and a mystery product, possibly P(NH2)2SF. [5]

Miscellaneous

PSF3 does not react with ether, benzene, carbon disulfide, or pure sulfuric acid. [5] It initiates tetrahydrofuran polymerization. [17]

PSF3 reacts with [SF6]− in a mass spectrometer to form [PSF4]−. [18]

PSF3 + [SF6]−• → PSF4− + SF5•

One fluorine can be substituted by iodine to give thiophosphoryl difluoride iodide, PSIF2. [19] PSIF2 can be converted to hydrothiophosphoryldifluoride, S=PHF2, by reducing it with hydrogen iodide. [20] In F2P(=S)−S−PF2, one sulfur forms a bridge between two phosphorus atoms. [19]

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. [21]

The critical point is at 346 K at 3.82 MPa. [22] The liquid refractive index is 1.353. [4]

The enthalpy of vaporisation 19.6 kJ/mol at boiling point. [23] The enthalpy of vaporisation at other temperatures is a function of temperature T: H(T)=28.85011(346-T)0.38 kJ/mol. [24]

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. [25]

The infrared spectrum includes vibrations at 275, 404, 442, 698, 951 and 983 cm−1. [26] These can be used to identify the molecule.

Related Research Articles

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

Oxygen difluoride is a chemical compound with the formula OF2. As predicted by VSEPR theory, the molecule adopts a bent molecular geometry. It is a strong oxidizer and has attracted attention in rocketry for this reason. With a boiling point of −144.75 °C, OF2 is the most volatile (isolable) triatomic compound. The compound is one of many known oxygen fluorides.

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

Manganese(III) fluoride (also known as Manganese trifluoride) is the inorganic compound with the formula MnF3. This red/purplish solid is useful for converting hydrocarbons into fluorocarbons, i.e., it is a fluorination agent. It forms a hydrate and many derivatives.

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

Thionyl fluoride is the inorganic compound with the formula SOF2. This colourless gas is mainly of theoretical interest, but it is a product of the degradation of sulfur hexafluoride, an insulator in electrical equipment. The molecule adopts a distorted pyramidal structure, with Cs symmetry. The S-O and S-F distances are 1.42 and 1.58 Å, respectively. The O-S-F and F-S-F angles are 106.2 and 92.2°, respectively.

<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 tetrafluoride 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">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

<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">Thiazyl fluoride</span> Chemical compound

Thiazyl fluoride, NSF, is a colourless, pungent gas at room temperature and condenses to a pale yellow liquid at 0.4 °C. Along with thiazyl trifluoride, NSF3, it is an important precursor to sulfur-nitrogen-fluorine compounds. It is notable for its extreme hygroscopicity.

Fluorination by sulfur tetrafluoride produces organofluorine compounds from oxygen-containing organic functional groups using sulfur tetrafluoride. The reaction has broad scope, and SF4 is an inexpensive reagent. It is however hazardous gas whose handling requires specialized apparatus. Thus, for many laboratory scale fluorinations diethylaminosulfur trifluoride ("DAST") is used instead.

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">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">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.

<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.

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 10 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 3 4 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.
  10. 1 2 3 Almasi, Lucreţia (1971). "The Sulfur–Phosphorus Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. pp. 79, 81. ISBN   0-8247-1615-9. LCCN   70-154612. Note the typo on p. 81: the final species in the final display should be PS2F−
    2    .
  11. ↑ 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.
  12. ↑ 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.
  13. ↑ 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.
  14. ↑ 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.
  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. ↑ 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 .
  17. ↑ 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.
  18. ↑ 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.
  19. 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.
  20. ↑ Charlton, Thomas L.; Cavell, R. G. (1968). "Preparation and properties of iodothiophosphoryl difluoride, SPF2I". Inorganic Chemistry. 7 (11): 2195. doi:10.1021/ic50069a005.
  21. ↑ 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.
  22. ↑ Handbook of Chemistry and Physics 87 ed page 6-39
  23. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 550. ISBN   978-0-8155-1495-4.
  24. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 406. ISBN   978-0-8155-1495-4.
  25. ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 685. ISBN   978-0-8155-1495-4.
  26. ↑ 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.

Other references

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