Chemistry:Phosphorothioc chloride difluoride
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| Names | |
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| IUPAC name
Difluorochloro(sulfanylidene)-λ5-phosphane
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| Other names
Phosphorothioic chloride difluoride, Chlorodifluorophosphine sulfide, Thiophosphoryl difluoride monochloride, Thiophosphoryl difluorochloride
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| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
PubChem CID
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| Properties | |
| PSClF2 | |
| 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 | |
| tetrahedron; | |
| Hazards | |
| Main hazards | toxic fumes |
| Related compounds | |
Related compounds
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Phosphoryl chloride difluoride Thiophosphoryl fluoride Phosphorothioc dichloride fluoride PSeF2Cl Thiophosphoryl chloride |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
Phosphorothioc 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°. The density of the gas at standard conditions is 5.579 g/L.[1] Critical pressure is 41.4 bars, and critical temperature is 439.2K.[2]
Production
Phosphorothioc 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)SP(CF3)2 or (CF3)2P(S)SPF2 react with chlorine.[5]
It can be formed from difluoro(germylthio)phosphine: PF2(SGeH3) + Cl2 → GeH3Cl + PClF2S[6]
Properties
Although phosphorothioc 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 vapourization 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 othophosphoric 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]
References
- ↑ Haynes, William M. (2016-04-19) (in en). CRC Handbook of Chemistry and Physics, 94th Edition. CRC Press. ISBN 9781466571150. https://books.google.com.au/books?id=MmDOBQAAQBAJ&pg=SA4-PA81.
- ↑ CRC Handbook of Chemistry and Physics. pp. 6–39.
- ↑ 3.0 3.1 3.2 "Advances in Inorganic Chemistry and Radiochemistry, Volume 2". 1960. https://books.google.com.au/books?id=KxuDjYsMLxMC&pg=PA129.
- ↑ Seel, Fritz; Ballreich, Kurt; Schmutzler, Reinhard (January 1962). "Darstellung von Säurefluoriden der Thiophosphonsäuren mittels Kaliumfluorsulfinats". Chemische Berichte 95 (1): 199–202. doi:10.1002/cber.19620950132.
- ↑ Doty, Leon F.; Cavell, Ronald G. (1 November 1974). "Mixed-valence derivatives of phosphorus sulfides. Two new isomeric thiophosphoryl-μ-thio-phosphines containing fluorine and trifluoromethyl substituents and a discussion of their exchange properties". Inorganic Chemistry 13 (11): 2722–2729. doi:10.1021/ic50141a035.
- ↑ .Ebsworth, E. A. V.; Macdonald, E. K.; Rankin, D. W. H. (1980). "The preparation, properties and gas-phase molecular structure of difluoro(germylthio)phosphine". Monatshefte für Chemie 111 (1): 221–233. doi:10.1007/BF00938730.
- ↑ Shimanouchi, T. (1973-04-01). "Tables of Molecular Vibrational Frequencies: Part 7". Journal of Physical and Chemical Reference Data 2 (2): 241. doi:10.1063/1.3253118. ISSN 0047-2689. Bibcode: 1973JPCRD...2..225S. http://aip.scitation.org/doi/10.1063/1.3253118.
- ↑ Durig, J. R.; Clark, J. W. (1967-04-15). "Vibrational Spectra of SPCl3, SPCl2F, SPClF2, and SPF3". The Journal of Chemical Physics 46 (8): 3057–3068. doi:10.1063/1.1841177. ISSN 0021-9606. Bibcode: 1967JChPh..46.3057D. http://aip.scitation.org/doi/10.1063/1.1841177.
- ↑ Horn, Hans-Georg; Müller, Achim (September 1966). "Untersuchungen an Phosphoryl- und Thiophosphorylverbindungen. IV.19F- und31P-kernmagnetische Resonanzspektren von SPF3, SPF2Cl und SPF2Br" (in de). Zeitschrift für anorganische und allgemeine Chemie 346 (5–6): 266–271. doi:10.1002/zaac.19663460506.
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