thiophosphoryl fluoride

Thiophosphoryl fluoride was discovered and named by J. W. Rodger and T. E. Thorpe in 1888.{{cite journal|doi=10.1039/CT8895500306|title=XXXIV.?On thiophosphoryl fluoride|year=1889|last1=Thorpe|first1=T. E.|last2=Rodger|first2=J. W.|journal=Journal of the Chemical Society, Transactions|volume=55|pages=306–323|url=https://zenodo.org/record/1754869}}{{cite journal|doi=10.1039/CT8885300766|title=LX.?Thiophosphoryl fluoride|year=1888|last1=Thorpe|first1=T. E.|last2=Rodger|first2=J. W.|journal=Journal of the Chemical Society, Transactions|volume=53|pages=766–767 |url=https://zenodo.org/record/2173570}}

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 {{chem2|PSCl3}} the proportion of {{chem2|PSF3}} was increased. They observed the spontaneous inflammability. They also used this method:

:{{chem2|3 PbF2 + P2S5 → 3 PbS + 2 PSF3}}

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

Another way to prepare {{chem2|PSF3}} is to add fluoride to {{chem2|PSCl3}} using sodium fluoride in acetonitrile.{{cite journal |doi=10.1016/S0022-1139(00)81660-7 |title=Investigations on the preparation, oxidation and reduction reactions of thiophosphoryl fluoride |year=1976 |last1=Padma |first1=D. K. |last2=Vijayalakshmi |first2=S. K. |last3=Vasudevamurthy |first3=A. R. |journal=Journal of Fluorine Chemistry |volume=8 |issue=6 |pages=461}}

A high yield reaction can be used to produce the gas:{{Citation needed|date=October 2019}}

:{{chem2|P4S10 + 12 HF → 6 H2S + 4 PSF3}}

Under high pressure phosphorus trifluoride can react with hydrogen sulfide to yield:{{cite journal|doi=10.1021/ic50181a007|title=High-pressure reactions of small covalent molecules. 10. The reaction of phosphorus trifluoride with hydrogen sulfide and sulfur dioxide|year=1978|last1=Hagen|first1=Arnulf P.|last2=Callaway|first2=Bill W.|journal=Inorganic Chemistry|volume=17|issue=3|pages=554}}

:{{chem2|PF3 + H2S → PSF3 + H2}} (1350 bar at 200 °C)

Another high pressure production uses phosphorus trifluoride with sulfur.

{{chem2|PSF3}} is unstable against moisture or heat. The pure gas is completely absorbed by alkali solutions, producing the fluoride and a thiophosphate ({{chem2|PSO3(3−)}}), but stable against CaO. The latter can be used to remove {{chem2|SiF4}} or {{chem2|PF3}} impurities.

Reaction with neutral water is slow:

:{{chem2|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.{{cite book|title=Sulfur in Organic and Inorganic Chemistry|volume=1|editor-first=Alexander|editor-last=Senning|year=1971|publisher=Marcel Dekker|location=New York|lccn=70-154612|isbn=0-8247-1615-9|first=Lucreţia|last=Almasi|chapter=The Sulfur–Phosphorus Bond|pages=79,81}} Note the typo on p. 81: the final species in the final display should be PS₂F{{su|b=2|p=−}}.

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

:{{chem2|PSF3 → S + PF3 → ...}}

Hot PSF₃ reacts with glass, producing {{chem2|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.

In air, PSF₃ burns spontaneously with a greyish green flame, producing solid white fumes containing {{chem2|SO2}} and {{chem2|P2O5}}. The flame is one of the coldest known. With dry oxygen, combustion may not be spontaneous and the flame is yellow.

Thiophosphoryl fluoride reduces oxygenated compounds to give phosphoryl fluoride and sulfur:{{cite journal|doi=10.1016/S0022-1139(00)85125-8|title=Reaction of thiophosphoryl fluoride with sulphur trioxide|year=1984|last1=Sampath Kumar|first1=H.P.|last2=Padma|first2=D.K.|last3=Vasudeva Murthy|first3=A.R.|journal=Journal of Fluorine Chemistry|volume=26|pages=117–123}}

:{{chem2|PSF3 + 3 SO3 → POF3 + 4 SO2}}

:{{chem2|2 PSF3 + SO2 → 2 POF3 + 3 S}}

The latter reaction also indicates why {{chem2|PSF3}} is not formed from {{chem2|PF3}} and {{chem2|SO2}}.

Various oxidants can convert thiophosphoryl fluoride to phosphorus dichloride trifluoride, e.g.:{{cite journal|doi=10.1016/S0022-1139(00)85026-5|title=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|year=1990|last1=Sampath Kumar|first1=H.P.|last2=Padma|first2=D.K.|journal=Journal of Fluorine Chemistry|volume=49|issue=3|pages=301}}

:{{chem2|PSF3 + 2 ICl → PCl2F3 + I2 + S}}.

Thiophosphoryl difluoride isocyanate can be formed by reacting {{chem2|PSF3}} with silicon tetraisocyanate at 200 °C in an autoclave.{{cite journal|doi=10.1016/0022-1902(70)80591-7|title=Thiophosphoryl-difluoride-isocyanate|year=1970|last1=Roesky|first1=H.W.|journal=Journal of Inorganic and Nuclear Chemistry|volume=32|issue=6|pages=1845–1846}}

In general, nucleophilic substitution onto thiophosphoryl fluoride is complex, because free fluoride ions tend to induce disproportionation to hexafluorophosphate and dithiodifluorophosphate ({{chem2|PS2F2−}}).{{cite journal|doi=10.1016/S0022-1139(00)80227-4|title=Quadruply bonded dimolybdenum complexes of PF₂S₂−. Comparison with complexes of PR₂S_2^p− (R = Et, Me)|year=1990|last1=Islam|first1=Mohammad Q.|last2=Hill|first2=William E.|last3=Webb|first3=Thomas R.|journal=Journal of Fluorine Chemistry|volume=48|issue=3|pages=429}} For example, with cesium fluoride:{{cite journal | doi=10.1021/ic50086a028 | title=Thiophosphate chemistry. Anion set X₂PS₂⁻, (XPS₂)2S²⁻, and (XPS₂)2S₂²⁻ | year=1970 | last1=Roesky | first1=Herbert W. | last2=Tebbe | first2=Fred N. | last3=Muetterties | first3=Earl L. | journal=Inorganic Chemistry | volume=9 | issue=4 | pages=831}}

:{{chem2|CsF + 2 PSF3 → Cs[PF6] + CsPS2F2}}

Thus {{chem2|PSF3}} combines with dimethylamine in solution to produce dimethylaminothiophosphoryl difluoride {{chem2|(H3C\s)2N\sP(\dS)F2}} and difluorophosphate and hexafluorophosphate ions:{{cite journal|doi=10.1139/v68-100|title=Chemistry of phosphorus fluorides. Part III. The reaction of thiophosphoryl-fluoride with dimethylamine and some properties of the dimethylaminothio- phosphoryl fluorides|year=1968|last1=Cavell|first1=R. G.|journal=Canadian Journal of Chemistry|volume=46|issue=4|pages=613–621|doi-access=free}}

: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 {{chem2|P(NH2)2SF}}.

{{chem2|PSF3}} does not react with ether, benzene, carbon disulfide, or pure sulfuric acid. It initiates tetrahydrofuran polymerization.{{cite journal|doi=10.1016/S0022-1139(00)81597-3|title=Thiophosphoryl fluoride and phosphoryl fluoride as initiators for the polymerisation of tetrahydrofuran|year=1978|last1=Padma|first1=D.K.|last2=Vijayalakshmi|first2=S.K.|journal=Journal of Fluorine Chemistry|volume=11|pages=51–56}}

{{chem2|PSF3}} reacts with {{chem2|[SF6]−}} in a mass spectrometer to form {{chem2|[PSF4]−}}.{{cite journal|doi=10.1016/0020-7381(71)85003-9|title=Reactions of gaseous inorganic negative ions: III. SF₆⁻ with POF₃ and PSF₃ |year=1971 |last1=Rhyne |first1=T |last2=Dillard |first2=J |journal=International Journal of Mass Spectrometry and Ion Physics |volume=7 |issue=5 |pages=371|bibcode=1971IJMSI...7..371R}}

:{{chem2|PSF3 + [SF6]^{-•} -> PSF4^{-} + SF5^{•} }}

One fluorine can be substituted by iodine to give thiophosphoryl difluoride iodide, {{chem2|PSIF2}}. {{chem2|PSIF2}} can be converted to hydrothiophosphoryldifluoride, {{chem2|S\dPHF2}}, by reducing it with hydrogen iodide.{{cite journal|doi=10.1021/ic50069a005|title=Preparation and properties of iodothiophosphoryl difluoride, SPF₂I |year=1968 |last1=Charlton |first1=Thomas L. |last2=Cavell |first2=R. G. |journal=Inorganic Chemistry |volume=7 |issue=11 |pages=2195}} In {{chem2|F2P(\dS)\sS\sPF2}}, one sulfur forms a bridge between two phosphorus atoms.{{cite journal|doi=10.1021/ic50081a037|title=Difluorothiophosphoryl-μ-thio-difluorophosphine and difluorophosphoryl-μ-oxo-difluorophosphine. Novel mixed-valence fluorophosphorus compounds|year=1969|last1=Charlton|first1=Thomas L.|last2=Cavell|first2=Ronald G.|journal=Inorganic Chemistry|volume=8|issue=11|pages=2436}}

Dimethylaminothiophosphoryl difluoride ({{chem2|(H3C\s)2N\sP(\dS)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 ({{chem2|(H3C\s)2N\sP(\dS)Cl2}}).

The thiophosphoryl trifluoride molecule shape has been determined using electron diffraction. The interatomic distances are P=S 0.187±0.003 nm, {{chem2|P\sF}} 0.153±0.002 nm and bond angles of {{chem2|F\sP\sF}} bonding is 100.3±2°, The microwave rotational spectrum has been measured for several different isotopologues.{{cite journal|doi=10.1063/1.1700162|title=Microwave Spectra and Molecular Structures of POF₃, PSF₃, POCl₃, and PSCl₃ |year=1952 |last1=Williams |first1=Quitman |last2=Sheridan |first2=John |last3=Gordy |first3=Walter |journal=The Journal of Chemical Physics |volume=20 |issue=1 |pages=164–167|bibcode=1952JChPh..20..164W}}

The critical point is at 346 K at 3.82 MPa.Handbook of Chemistry and Physics 87 ed page 6-39 The liquid refractive index is 1.353.{{Cite web |url=http://hgspace.com/chemical-dictionary/cas/m5/2404-52-6.html |title=Phosphorothioic trifluoride-(2404-52-6)-Chemical Dictionary-hgspace.com |access-date=2012-01-29 |archive-date=2016-03-03 |archive-url=https://web.archive.org/web/20160303234552/http://hgspace.com/chemical-dictionary/cas/m5/2404-52-6.html |url-status=dead}}

The enthalpy of vaporisation 19.6 kJ/mol at boiling point.{{cite book | url = https://books.google.com/books?id=31O4upzTHQwC&pg=PA550| page =550 | title = The foundations of vacuum coating technology | isbn = 978-0-8155-1495-4 | last1 = Mattox | first1 = D. M. | date = 2003-12-31| publisher =Elsevier Science }} The enthalpy of vaporisation at other temperatures is a function of temperature T: H(T)=28.85011(346-T)^0.38 kJ/mol.{{cite book | url=https://books.google.com/books?id=31O4upzTHQwC&pg=PA406| page=406 | title=The foundations of vacuum coating technology | isbn =978-0-8155-1495-4 | last1=Mattox | first1 =D. M. | date =2003-12-31| publisher=Elsevier Science }}

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.{{cite book | url =https://books.google.com/books?id=31O4upzTHQwC&pg=PA685| page =685 | title =The foundations of vacuum coating technology | isbn =978-0-8155-1495-4 | last1 =Mattox | first1 =D. M. | date =2003-12-31| publisher =Elsevier Science }}

The infrared spectrum includes vibrations at 275, 404, 442, 698, 951 and 983 cm⁻¹.{{cite journal|doi=10.1016/0584-8539(67)80227-7|title=The infrared spectrum of thiophosphoryl fluoride|year=1967|last1=Cavell|first1=R|journal=Spectrochimica Acta Part A: Molecular Spectroscopy|volume=23|issue=2|pages=249–256|bibcode=1967AcSpA..23..249C}} These can be used to identify the molecule.

{{Reflist|2}}

• {{cite journal | journal = Transactions of the Faraday Society | volume = 35 | year = 1963 | page = 137 | doi = 10.1039/df9633500137 | title=Absorption spectrum of chlorine dioxide in the vacuum ultra-violet| last1 = Humphries | first1 = C. M. | last2 = Walsh | first2 = A. D. | last3 = Warsop | first3 = P. A.}}
• {{cite journal| doi=10.1063/1.432929| title=19F and 31P magnetic shielding anisotropies and the F–P–F bond angle of PSF3 in a smectic liquid crystal solvent| year=1976| last1=Montana| first1=Anthony J.| last2=Zumbulyadis| first2=Nikolaos| last3=Dailey| first3=Benjamin P.| journal=The Journal of Chemical Physics| volume=65| issue=11| pages=4756| bibcode=1976JChPh..65.4756M}}
• {{cite book | url =https://books.google.com/books?id=0vv5GwAACAAJ | title =The structure of PSF3 and POF3 from microwave spectroscopy | last1 =Hawkins | first1 =Norval John | year =1951}}
• {{cite web | url =http://webbook.nist.gov/cgi/cbook.cgi?ID=C2404526&Units=SI&Mask=7 | title =Thiophosphoryl fluoride | year =1998 | pages =1–1951 | publisher = NIST| last1 =Chase | first1 =M. W.}}
• {{cite journal | doi=10.1063/1.1700162 | title=Microwave Spectra and Molecular Structures of POF3, PSF3, POCl3, and PSCl3 | year=1952 | last1=Williams | first1=Quitman | last2=Sheridan | first2=John | last3=Gordy | first3=Walter | journal=The Journal of Chemical Physics | volume=20 | issue=1 | pages=164–167| bibcode=1952JChPh..20..164W}}
• {{cite journal|doi=10.1002/cber.19380710419|title=Zur Kenntnis des Phosphorsulfotrifluorids PSF3 und über ein Salz der Thiodifluorphosphorsäure H\PSF2O]|year=1938|last1=Lange|first1=Willy|last2=Askitopoulos|first2=Konstantin|journal=Berichte der Deutschen Chemischen Gesellschaft (A and B Series)|volume=71|issue=4|pages=801}}
• {{cite journal | first = C. |last= Poulenc |title= Comptes rendus hebdomadaires des séances de l'Académie des sciences / Publiés... Par MM. Les secrétaires perpétuels | year= 1891 | journal =Comptes Rendus | volume= 113 | pages= 75 | url = http://gallica.bnf.fr/ark:/12148/bpt6k30691/f75.image}}

Category:Phosphorus halides

Category:Thiophosphoryl compounds