Phosphorothioic chloride difluoride

Phosphorothioic chloride difluoride or thiophosphoryl chloride difluoride is a chemical compound with formula PSClF₂. It is normally found as a gas boiling at 6.3 °C and melting at −155.2 °C. The density of the gas at standard conditions is 5.579 g/L.^[1] Critical pressure is 41.4 bars, and critical temperature is 439.2 K.^[2]

Phosphorothioic chloride difluoride

Names
IUPAC name Phosphorothioic chloride difluoride
Systematic IUPAC name Difluorochloro(sulfanylidene)-λ5-phosphane
Other names Chlorodifluorophosphine sulfide Phosphorothioic chloride difluoride Thiophosphoryl difluoride monochloride Thiophosphoryl difluorochloride TL-152
Identifiers
CAS Number	2524-02-9 N
3D model (JSmol)	Interactive image
ChemSpider	171176 N
PubChem CID	197765
RTECS number	XN2990000
CompTox Dashboard (EPA)	DTXSID50179896
InChI InChI=1S/ClF2PS/c1-4(2,3)5 N[pubchem] Key: PBDMSMPIDQNREV-UHFFFAOYSA-N N
SMILES FP(=S)(F)Cl
Properties
Chemical formula	PSClF2
Molar mass	136.48 g·mol−1
Appearance	Colorless gas or liquid
Density	5.579 g/L as gas
Melting point	−155.2 °C (−247.4 °F; 118.0 K)
Boiling point	6.3 °C (43.3 °F; 279.4 K)
Structure
Molecular shape	Tetrahedral at the P atom
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	toxic fumes
Related compounds
Related compounds	Phosphoryl chloride difluoride Phosphorothioic dichloride fluoride Phosphoryl chloride difluoride Selenophosphoryl chloride difluoride Thiophosphoryl fluoride Thiophosphoryl chloride Thiophosphoryl bromide Thiophosphoryl iodide Phosphoryl chloride Phosphoryl fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Production

Phosphorothioic chloride difluoride was made in 1940 by reacting PSCl₃ with SbF₃ and SbCl₅ at 75 °C.^[3]

In another reaction PSCl₃ reacts with KSO₂F to make PSF₃, KCl and SO₂, but also partly yields PSClF₂.^[4]

A small percentage of is formed when F₂P(=S)−S−P(−CF₃)₂ or (F₃C−)₂P(=S)−S−PF₂ reacts with chlorine.^[5]

It can be formed from difluoro(germylthio)phosphine:

F₂P−S−GeH₃ + Cl₂ → GeH₃Cl + S=PClF₂^[6]

Properties

Although phosphorothioic chloride difluoride does not spontaneously ignite in air, mixtures with air are explosive. The gas is hydrolysed slowly by water vapour. It also reacts with potassium hydroxide solution.^[3]

Heat of vaporization is 5703 cal/mol.^[3]

Infrared bands in the gas are at 946, 920, 738, 541, 395, 361, 317, missed, and 198 cm⁻¹. In liquid, a Raman spectroscopy has bands at 939, 913, 727, 536, 394, 359, 314, 251, 207. These are for PF₂ symmetric stretch in a' and a'' symmetry, PS stretch, PCl stretch, PCl bend, PF₂ scissor, PF₂ rock, PS op-bend, and PS ip-bend.^[7][8]

The nuclear magnetic resonance coupling constants for ³¹P are 1220. It is a triplet line with intensities 1:2:1. The chemical shift from orthophosphoric acid is −50×10⁻⁶. For ¹⁹F the coupling constant is 1218. It is a doublet line in ratio 1:1. The chemical shift from CCl₃F is −15.9×10⁻⁶.^[9]