Chemistry:Thiophosphoryl fluoride
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| IUPAC name
Trifluoro(sulfanylidene)-λ5-phosphane
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| Other names | |||
| Identifiers | |||
3D model (JSmol)
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PubChem CID
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| Properties | |||
| PSF 3 | |||
| Molar mass | 120.035 g/mol | ||
| Appearance | Colorless 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 | |||
| Main hazards | Spontaneously flammable in air; toxic fumes | ||
| Flash point | very low | ||
| Related compounds | |||
Related compounds
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |||
| Infobox references | |||
Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF
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]
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 PSCl
3 the proportion of PSF
3 was increased. They observed the spontaneous inflammability. They also used this method:
- 3 PbF
2 + P
2S
5 → 3 PbS + 2 PSF
3
at 170 °C, and also substituting a mixture of red phosphorus and sulfur, and substituting bismuth trifluoride.[5]
Another way to prepare PSF
3 is to add fluoride to PSCl
3 using sodium fluoride in acetonitrile.[8]
- P
4S
10 + 12 HF → 6 H
2S + 4 PSF
3
Under high pressure phosphorus trifluoride can react with hydrogen sulfide to yield:[9]
- PF
3 + H
2S → PSF
3 + H
2 (1350 bar at 200 °C)
Another high pressure production uses phosphorus trifluoride with sulfur.[9]
Reactions
PSF
3 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 SiF
4 or PF
3 impurities.[5]
Hydrolysis and decomposition
Reaction with neutral water is slow:
- PSF
3 + 4 H
2O → H
2S + H
3PO
4 + 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:
- PSF
3 → S + PF
3 → ...
Hot PSF3 reacts with glass, producing SF
4, 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 SO
2 and P
2O
5. 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]
- PSF
3 + 3 SO
3 → POF
3 + 4 SO
2 - 2 PSF
3 + SO
2 → 2 POF
3 + 3 S
The latter reaction also indicates why PSF
3 is not formed from PF
3 and SO
2.[9]
Various oxidants can convert thiophosphoryl fluoride to phosphorus dichloride trifluoride, e.g.:[12]
- PSF
3 + 2 ICl → PCl
2F
3 + I
2 + S.
Nucleophilic substitution
Thiophosphoryl difluoride isocyanate can be formed by reacting PSF
3 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 (PS
2F−
2).[10][14] For example, with cesium fluoride:[15]
- CsF + 2 PSF
3 → Cs[PF
6] + CsPS
2F
2
Thus PSF
3 combines with dimethylamine in solution to produce dimethylaminothiophosphoryl difluoride (H
3C–)
2N–P(=S)F
2 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(NH
2)
2SF.[5]
Miscellaneous
PSF
3 does not react with ether, benzene, carbon disulfide, or pure sulfuric acid.[5] It initiates tetrahydrofuran polymerization.[17]
PSF
3 reacts with [SF
6]−
in a mass spectrometer to form [PSF
4]−
.[18]
- PSF
3 + [SF
6]-•
→ PSF
4-
+ SF
5•
Related compounds
One fluorine can be substituted by iodine to give thiophosphoryl difluoride iodide, PSIF
2.[19] PSIF
2 can be converted to hydrothiophosphoryldifluoride, S=PHF
2, by reducing it with hydrogen iodide.[20] In F
2P(=S)–S–PF
2, one sulfur forms a bridge between two phosphorus atoms.[19]
Dimethylaminothiophosphoryl difluoride ((H
3C–)
2N–P(=S)F
2) 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 ((H
3C–)
2N–P(=S)Cl
2).
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.
References
- ↑ 1.0 1.1 A likely spelling mistake in Handbook of Chemistry and Physics 87 ed
- ↑ "FP(F)(F)=S". http://www.chemicalize.org/structure/#!mol=FP%28F%29%28F%29%3DS&source=fp.
- ↑ "phosphorothioic trifluoride". http://www.chemicalize.org/structure/#!mol=FP%28F%29%28F%29%3DS&source=fp.
- ↑ 4.0 4.1 "Phosphorothioic trifluoride-(2404-52-6)-Chemical Dictionary-hgspace.com". http://hgspace.com/chemical-dictionary/cas/m5/2404-52-6.html.
- ↑ 5.00 5.01 5.02 5.03 5.04 5.05 5.06 5.07 5.08 5.09 Thorpe, T. E.; Rodger, J. W. (1889). "XXXIV.?On thiophosphoryl fluoride". Journal of the Chemical Society, Transactions 55: 306–323. doi:10.1039/CT8895500306. https://zenodo.org/record/1754869.
- ↑ Banks, Ronald Eric (2000). Fluorine chemistry at the millennium: fascinated by fluorine. Elsevier. p. 502. ISBN 0-08-043405-3. https://books.google.com/books?id=PKegfJ_fVBMC&pg=PA502.
- ↑ Thorpe, T. E.; Rodger, J. W. (1888). "LX.?Thiophosphoryl fluoride". Journal of the Chemical Society, Transactions 53: 766–767. doi:10.1039/CT8885300766. https://zenodo.org/record/2173570.
- ↑ 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.
- ↑ 9.0 9.1 9.2 9.3 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.
- ↑ 10.0 10.1 10.2 Almasi, Lucreţia (1971). "The Sulfur–Phosphorus Bond". in Senning, Alexander. Sulfur in Organic and Inorganic Chemistry. 1. New York: Marcel Dekker. pp. 79,81. ISBN 0-8247-1615-9. Note the typo on p. 81: the final species in the final display should be PS2F−2.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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. doi:10.1016/0020-7381(71)85003-9. Bibcode: 1971IJMSI...7..371R.
- ↑ 19.0 19.1 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.
- ↑ Charlton, Thomas L.; Cavell, R. G. (1968). "Preparation and properties of iodothiophosphoryl difluoride, SPF2I". Inorganic Chemistry 7 (11): 2195. doi:10.1021/ic50069a005.
- ↑ 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. doi:10.1063/1.1700162. Bibcode: 1952JChPh..20..164W.
- ↑ Handbook of Chemistry and Physics 87 ed page 6-39
- ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 550. ISBN 978-0-8155-1495-4. https://books.google.com/books?id=31O4upzTHQwC&pg=PA550.
- ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 406. ISBN 978-0-8155-1495-4. https://books.google.com/books?id=31O4upzTHQwC&pg=PA406.
- ↑ Mattox, D. M. (2003-12-31). The foundations of vacuum coating technology. Elsevier Science. p. 685. ISBN 978-0-8155-1495-4. https://books.google.com/books?id=31O4upzTHQwC&pg=PA685.
- ↑ Cavell, R (1967). "The infrared spectrum of thiophosphoryl fluoride". Spectrochimica Acta Part A: Molecular Spectroscopy 23 (2): 249–256. doi:10.1016/0584-8539(67)80227-7. Bibcode: 1967AcSpA..23..249C.
Other references
- Humphries, C. M.; Walsh, A. D.; Warsop, P. A. (1963). "Absorption spectrum of chlorine dioxide in the vacuum ultra-violet". Transactions of the Faraday Society 35: 137. doi:10.1039/df9633500137.
- Montana, Anthony J.; Zumbulyadis, Nikolaos; Dailey, Benjamin P. (1976). "19F and 31P magnetic shielding anisotropies and the F–P–F bond angle of PSF3 in a smectic liquid crystal solvent". The Journal of Chemical Physics 65 (11): 4756. doi:10.1063/1.432929. Bibcode: 1976JChPh..65.4756M.
- Hawkins, Norval John (1951). The structure of PSF3 and POF3 from microwave spectroscopy. https://books.google.com/books?id=0vv5GwAACAAJ.
- Chase, M. W. (1998). "Thiophosphoryl fluoride". NIST. pp. 1–1951. http://webbook.nist.gov/cgi/cbook.cgi?ID=C2404526&Units=SI&Mask=7.
- 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. doi:10.1063/1.1700162. Bibcode: 1952JChPh..20..164W.
- Lange, Willy; Askitopoulos, Konstantin (1938). "Zur Kenntnis des Phosphorsulfotrifluorids PSF3 und über ein Salz der Thiodifluorphosphorsäure H\PSF2O]". Berichte der Deutschen Chemischen Gesellschaft (A and B Series) 71 (4): 801. doi:10.1002/cber.19380710419.
- Poulenc, C. (1891). "Comptes rendus hebdomadaires des séances de l'Académie des sciences / Publiés... Par MM. Les secrétaires perpétuels". Comptes Rendus 113: 75. http://gallica.bnf.fr/ark:/12148/bpt6k30691/f75.image.
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