Pentafluorosulfate(IV)
.svg.png) Chemical structure of pentafluorosulfate(IV) anion | |
| Identifiers | |
|---|---|
3D model (JSmol) |
|
| |
| |
| Properties | |
| F5S− | |
| Molar mass | 127.05 g·mol−1 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references | |
Pentafluorosulfite or pentafluorosulfate(IV) is an anion with formula [SF5]−.
Most pentafluorosulfite salts are unstable, decaying info SF4 gas and a fluoride salt. So for example, tetramethyl ammonium pentafluorosulfite has a vapour pressure of 2-3 mm Hg of SF4.[1]
Formation
Some salts can be formed by reacting SF4 gas at low temperature with the fluoride salt.[1]
Properties
[[]] Pentafluorosulfites are decomposed by water, but may be soluble in dimethylformamide.[1]
The ion has a square pyramidal shape with C4v symmetry.[2] The ion has a very similar spectrum and force constants to ClF5, and the spectrum is similar in form to other pentafluorides with a lone pair of electrons.[2]
Force constants derived from the IR and Raman spectrum are: fR = 4.12 mdyn/Å, fr = 2.06 mdyn/Å, fα = 2.26 mdyn/Å radian, fβ = 0.86 mdyn/Å radian, frr' = 0.52, fββ' = 0.55 mdyn/Å radian, fαα' = 0.11 mdyn/Å radian, frr =0.23 mdyn/Å radian, fRβ =0.25mdyn/Å radian, frβ =0.15, frβ mdyn/Å radian, fββ = −0.20 mdyn/Å radian2.[2]
| point group assignment | description | band id | IR band cm−1 | Raman line cm−1 |
|---|---|---|---|---|
| A1 | vibration S-F axial | v1 | 793 | 796 |
| A1 | vibration S-F4 equatorial | v2 | 520 | 522 |
| A1 | deformation S-F4 umbrella | v3 | 466 | 469 |
| B1 | stretch S-F4 out of phase | v4 | - | 435 overlap |
| B1 | S-F4 out of plane | v5 | - | 269 |
| B2 | deformation S-F4 in plane | v6 | - | 342 |
| E | vas | v7 | 590 | 590 |
| E | deformation F'-S-F4 | v8 | 430 | 435 overlap |
| E | deformation as SF4 in plane | v9 | - | 241 |
Reactions
Trichloroisocyanuric acid can react with pentafluorosulfite to form SF5Cl.[3]
Related
Selenium and tellurium also form similar anions SeF−5 and TeF−5.[2] The general term for these is pentafluorochalcogenate(IV) anions.[2] In organic chemistry the -SF5 group is called pentafluoro-λ6-sulfane or pentafluorosulfane, or as a prefix: pentafluoro-λ6-sulfanyl or pentafluorosulfanyl.[4]
List
| formula | crystal system | space group | unit cell | cell volume | density | comment | ref |
|---|---|---|---|---|---|---|---|
| [(CH3)4N+]SF5− | tetragonal | P4/n | a=13.503 c=19.471 Z=4 | 3550.2 | 1.48 | [1] | |
| [(tmg)3PF]+SF5− tmg=tetramethylguanidyl | dissolve in THF or 1,2-difluorobenzene | [5] | |||||
| [(R1)3PF]+SF5− R1 = 1,3-di-tert-butylimidazolidin-2-ylidenamino | [5] | ||||||
| Rb+SF5− | orthorhombic | Pbnm | a = 7.76 b = 9.903 c = 6.141 Z = 4 | [6] | |||
| trans,trans-[Rh(Cl)2(CO)(IMes)2][SF5] | deep red; decomposes at room temperature | [7] | |||||
| trans-[Rh(Cl)(F)(CO)(IMes)2][SF5] | decomposes at room temperature | [7] | |||||
| Cs+SF5− | tetrahedral | P4b2 | a = 10.32 c = 6.276 Z = 1 | [6] | |||
| (Cs+)6(SF5−)4 (HF2−)2 | [6] | ||||||
| [Cs+.(18-crown-6)2] [SF5−] | [8] | ||||||
| [Cs(tetraglyme)2][SF5] | tetrahedral | P421c | a =13.1515 c=17.792 | [9] |
References
- 1 2 3 4 Tunder, R.; Siegel, B. (September 1963). "The SF5 anion". Journal of Inorganic and Nuclear Chemistry. 25 (9): 1097–1098. doi:10.1016/0022-1902(63)80128-1.
- 1 2 3 4 5 6 Christe, Karl O.; Curtis, E. C.; Schack, Carl J.; Pilipovich, D. (July 1972). "Vibrational spectra and force constants of the square-pyramidal anions SF5-, SeF5-, and TeF5-". Inorganic Chemistry. 11 (7): 1679–1682. doi:10.1021/ic50113a046.
- ↑ Eder, Tobias; Buß, Florenz; Wilm, Lukas F. B.; Seidl, Michael; Podewitz, Maren; Dielmann, Fabian (2022-10-17). "Oxidative Fluorination of Selenium and Tellurium Compounds using a Thermally Stable Phosphonium SF5− Salt Accessible from SF6". Angewandte Chemie. 134 (42) e202209067. Bibcode:2022AngCh.13409067E. doi:10.1002/ange.202209067. ISSN 0044-8249.
- ↑ Chan, Julian M. W. (2019). "Pentafluorosulfanyl group: an emerging tool in optoelectronic materials". Journal of Materials Chemistry C. 7 (41): 12822–12834. doi:10.1039/C9TC01949A.
- 1 2 Röthel, Maike B.; Schöler, Andreas; Buß, Florenz; Löwe, Pawel; Dielmann, Fabian (2024-10-08). "Phosphonium SF5− Salts Derived from Sulfur Hexafluoride as Deoxyfluorination Reagents". Chemistry – A European Journal. 30 (56) e202402028. doi:10.1002/chem.202402028. ISSN 0947-6539. PMID 38958451.
- 1 2 3 Bittner, J.; Fuchs, J.; Seppelt, K. (February 1988). "Die Kristallstruktur des SF5− -Anions". Zeitschrift für anorganische und allgemeine Chemie. 557 (1): 182–190. Bibcode:1988ZAACh.557..182B. doi:10.1002/zaac.19885570119.
- 1 2 Jaeger, Ruben; Talavera, Maria; Braun, Thomas (July 2021). "Studies on the reactivity of Rh(I) complexes towards SF5Cl". Journal of Fluorine Chemistry. 247 109803. doi:10.1016/j.jfluchem.2021.109803.
- ↑ Clark, M.; Kellen-Yuen, C. J.; Robinson, K. D.; Zhang, H.; Yang, Z. Y.; Madappat, K. V.; Fuller, J. W.; Atwood, J. L.; Thrasher, J. S. (1992). "'Naked' SF5− anion: the crystal and molecular structure of [Cs+.(18-crown-6)2] [SF5-]". European Journal of Solid State and Inorganic Chemistry. 29 (4–5): 809–833.
- ↑ Matsumoto, Kazuhiko; Haruki, Yuki; Sawada, Shunsuke; Yamada, Shigeyuki; Konno, Tsutomu; Hagiwara, Rika (2018-12-03). "Stabilization of SF5– with Glyme-Coordinated Alkali Metal Cations". Inorganic Chemistry. 57 (23): 14882–14889. doi:10.1021/acs.inorgchem.8b02655. hdl:2433/245207. ISSN 0020-1669. PMID 30444364.