Chemistry:Difluorodithiophosphate
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A difluorodithiophosphate is an anion or chemical compound with phosphorus connected to two sulfur atoms and two fluorine atoms. It has a single negative charge. The formula is [S2PF2]−.
Related compounds are the fluorodithiophosphates,[1] difluoropentathiodiphosphates ([S5P2F2]2–), fluorotrithiophosphates ([S3PF]2–)[2] and the difluorothiophosphates (F2P(O)S−). Fluorine can also be substituted by trifluoromethyl, phenyl, methyl or ethoxy groups.[3]
Formation
Salts containing difluorodithiophosphate can be made by reacting difluorodithiophosphoric acid (HS2PF2) with electropositive metals. Less electropositive metals salts may be produced by a reaction of the acid with the metal oxide or chloride.[4]
Other ways it can be produced are in a reaction of dimethylamine with thiophosphoryl fluoride (SPF3).[5]
Properties
Thermal decomposition of difluorodithiopgosphate salts yields thiophosphoryl fluoride and phosphorus trifluoride.[6]
Some compounds with two or three difluorodithiophospate groups are monomeric, dissolving in benzene, and being quite volatile, meaning they can be sublimed.[4] Other solvents include toluene, heptane and 1,2-dichloroethane.[7]
List
| formula | name | crystal | space group | unit cell | volume | density | comment | ref |
|---|---|---|---|---|---|---|---|---|
| H[S2PF2] | difluorodithiophosphoric acid | liquid | boil 72°; colourless | [8] | ||||
| [(C3H7)4N][S2PF2] | tetrapropylammonium difluorodithiophosphate | orthorhombic | Pbca | a=14.9466 b=14.6702 c=16.8033 Z=8 | 3684.5 | 1.151 | [9] | |
| (CH3)3SiSP(S)F2 | trimethylsilyl difluorodithiophosphate | −79.7° | [10] | |||||
| [(C6H5)4PS2PF2 | [11] | |||||||
| KS2PF2 | [11] | |||||||
| Cl3Ti[S2PF2] | [12] | |||||||
| V[S2PF2]3 | tris(difluorodithio-phosphinato)vanadium (111) | deep red-brown; mp ~46.5 | [13][14] | |||||
| OV[S2PF2]2 | black | [13][14][3] | ||||||
| Cr[S2PF2]3 | deep purple; volatile; mp 52° | [4] | ||||||
| Mn[S2PF2]2 | pink | [4] | ||||||
| Mn(CO)3P(C6H5)3S2PF2 | yellow; melt ~119° | [15] | ||||||
| Mn(CO)3P(C6H5)2C2H4P(C6H5)2SP(S)F2 | yellow-orange | [15] | ||||||
| Fe[S2PF2]2 | tan mp=~80°C | [4] | ||||||
| π-C5H5Fe(CO)2S2PF2 | pi-cyclopentadienyl iron dicarbonyl difluorodithiophosphate | yellow-brown; decompose 95°C | [16] | |||||
| (ON)2Fe[S2PF2] | rusty-red; mp 69-70° | [4] | ||||||
| Co[S2PF2]2 | green; mp=44° volatile | [4] | ||||||
| (ON)2Co[S2PF2] | brown | [4] | ||||||
| Co[S2PF2]3 | brown mp 34° volatile | [4] | ||||||
| Ni[S2PF2]2 | dark green mp ~43° volatile | [4] | ||||||
| Cu[S2PF2] | off-white dec >400° | [4] | ||||||
| (Ph3P)2Cu[S2PF2] | white dec 200° | [4] | ||||||
| Zn[S2PF2]2 | mp ~157° | [4] | ||||||
| Cl3Nb[S2PF2] | ochre coloured | [12] | ||||||
| Cl3Nb[S2PF2]2 | trichlorobis(difluorodithio-phosphinato)niobium(Y) | orange | [12] | |||||
| Mo[S2PF2]3 | red; mp 62°; volatile | [17] | ||||||
| OMo[S2PF2]2 | green | [17] | ||||||
| π-C5H5Mo(CO)3SP(S)F2 | red-orange; decompose ~ 102°C | [15] | ||||||
| π-C5H5Mo(CO)2S2PF2 | purple; melt 39° | [15] | ||||||
| Pd[S2PF2]2 | orange mp 56.5° volatile | [4] | ||||||
| (Ph3P)Pd[S2PF2]2 | orange mp 141° | [4] | ||||||
| (Ph3P)2Pd[S2PF2]2 | yellow dec 160° | [4] | ||||||
| (p-Me-Ph3P)Pd[S2PF2]2 | orange 189° | [4] | ||||||
| (p-Me-Ph3P)2Pd[S2PF2]2 | yellow dec 172° | [4] | ||||||
| (Ph3As)Pd[S2PF2]2 | orange mp 122° | [4] | ||||||
| (n-C3H7)4NPd[S2PF2]3 | yellow dec 160° | [4] | ||||||
| Rh[S2PF2]3 | volatile | [4] | ||||||
| Rh(CO)2[S2PF2] | orange-red; mp 48° | [18] | ||||||
| Rh(CO)(P(C6H5)3)[S2PF2] | yellow | [18] | ||||||
| Rh(CO)(As(C6H5)3)[S2PF2] | brownish-red | [18] | ||||||
| Rh(CO)(Sb(C6H5)3)[S2PF2] | brownish-red | [18] | ||||||
| Ru[S2PF2]3 | reddish-orange mp 54° | [4] | ||||||
| RuH(CO)(S 2PF 2)(PPh 3) 2 |
triclinic | P-1 | a=11.127 b=12.345 !!! c=13.689 α=88.239° β=81.183° γ=76.965° Z=2 | 1810.2 | 1.489 | [9] | ||
| RuCl(CO)(S 2PF 2)(PPh 3) 2 |
monoclinic | P21/c | a=17.325 b=10.1385 c=20.967 β=104.443° Z=4 | 3566 | 1.531 | [9] | ||
| Ru(S 2PF 2) 2(PPh 3) 2 |
monoclinic | C2/c | a=39.987 b=9.9967 c=21.910 β=116.810° Z=8 | 7731.0 | 1.601 | [9] | ||
| Ru(CO)(η1-S2PF2)(η2-S2PF2)(PPh3)2 | cis | triclinic | P-1 | a=12.271 b=13.058 c=15.012 α=80.397° β=82.335° γ=63.243° | 2113.1 | 1.595 | [9] | |
| Ru(CO)(η1-S2PF2)(η2-S2PF2)(PPh3)2 | trans | monoclinic | P21/n | a=13.279 b=20.031 c=15.762 β=91.664° Z=4 | 4191.0 | 1.589 | [9] | |
| Ag[S2PF2] | white mp ~150° | [4] | ||||||
| Cd[S2PF2]2 | dec 173° | [4] | ||||||
| (CH3)2ClSnSP(S)F2 | dimethylstannyl chloride difluorodithiophosphate | melt 6.4° | [10] | |||||
| CsS2PF2 | dec 298° | [11] | ||||||
| Cl3Ta[S2PF2]2 | yellow | [12] | ||||||
| OWCl[S2PF2]2 | olive brown | [17] | ||||||
| Cl2W[S2PF2]3 | brown | [17] | ||||||
| π-C5H5W(CO)3SP(S)F2 | rust coloured; dec 75° | [15] | ||||||
| Pt[S2PF2]2 | yellow mp ~53.5° volatile | [4] | ||||||
| (Ph3P)Au[S2PF2] | mp 98° | [4] | ||||||
| Hg[S2PF2]2 | dec 163° | [4] | ||||||
| Ph=phenyl; Me=methyl | g/cc | mp = melting point °C
dec = decomposes |
References
- ↑ Pan, Song; Chen, Chong; Liang, Qing-Wen; Jia, Ai-Quan; Zhang, Qian-Feng (February 2025). "Synthesis, structures and photocatalytic properties of two binuclear sulfur-bridged cymene-ruthenium fluorodithiophosphates". Journal of Organometallic Chemistry 1025. doi:10.1016/j.jorganchem.2024.123481.
- ↑ Gaydon, Quentin; Bohle, David Scott (3 October 2022). "Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d 8 and d 6 Complexes of [η 2 -S 3 PF] 2–". Inorganic Chemistry 61 (39): 15359–15367. doi:10.1021/acs.inorgchem.2c01692. PMID 36121761.
- ↑ 3.0 3.1 Cavell, R. G.; Day, E. D.; Byers, W.; Watkins, P. M. (July 1972). "Metal complexes of substituted dithiophosphinic acids. III. Vanadyl complexes" (in en). Inorganic Chemistry 11 (7): 1591–1597. doi:10.1021/ic50113a027. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50113a027.
- ↑ 4.00 4.01 4.02 4.03 4.04 4.05 4.06 4.07 4.08 4.09 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 4.24 4.25 4.26 Tebbe, Fred N.; Muetterties, E. L. (March 1970). "Metal complexes of the difluorodithiophosphate ligand" (in en). Inorganic Chemistry 9 (3): 629–637. doi:10.1021/ic50085a040. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50085a040.
- ↑ Cavell, R. G. (15 February 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.
- ↑ Roesky, Herbert W.; Tebbe, Fred N.; Muetterties, Earl L. (April 1970). "Thiophosphate chemistry. Anion set X2PS2-, (XPS2)2S2-, and (XPS2)2S22-" (in en). Inorganic Chemistry 9 (4): 831–836. doi:10.1021/ic50086a028. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50086a028.
- ↑ Tebbe, Fred N.; Roesky, Herbert W.; Rode, W. C.; Muetterties, E. L. (June 1968). "New sulfur chelate chemistry". Journal of the American Chemical Society 90 (13): 3578–3579. doi:10.1021/ja01015a058.
- ↑ Charlton, Thomas L.; Cavell, Ronald G. (February 1969). "Synthesis and properties of difluorodithiophosphoric acid" (in en). Inorganic Chemistry 8 (2): 281–285. doi:10.1021/ic50072a020. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50072a020.
- ↑ 9.0 9.1 9.2 9.3 9.4 9.5 Gaydon, Quentin; Bohle, David Scott (19 August 2022). "Organometallic Chemistry of the Difluorodithiophosphate Anion". European Journal of Inorganic Chemistry 2022 (23). doi:10.1002/ejic.202200164.
- ↑ 10.0 10.1 Lustig, Max; McKennon, D. W. (February 1971). "Group IVA alkylmetal difluorodithiophosphates" (in en). Inorganic Chemistry 10 (2): 406–407. doi:10.1021/ic50096a044. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50096a044.
- ↑ 11.0 11.1 11.2 Lustig, Max; Ruff, John K. (November 1967). "Nonmetal oxy- and thiofluoride salts" (in en). Inorganic Chemistry 6 (11): 2115–2117. doi:10.1021/ic50057a044. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50057a044.
- ↑ 12.0 12.1 12.2 12.3 Cavell, R. G.; Sanger, A. R. (September 1972). "Metal complexes of substituted dithiophosphinic acids. VII. Reactions of titanium tetrachloride, vanadium tetrachloride, niobium tetrachloride, niobium pentachloride, and tantalum pentachloride" (in en). Inorganic Chemistry 11 (9): 2016–2019. doi:10.1021/ic50115a006. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50115a006.
- ↑ 13.0 13.1 Wasson, John R.; Woltermann, Gerald M.; Stoklosa, Henry J. (1973), "Transition metal dithio- and diselenophosphate complexes" (in en), Inorganic Chemistry (Berlin/Heidelberg: Springer-Verlag) 35/1: pp. 65–129, doi:10.1007/bfb0051359, ISBN 978-3-540-06080-2, http://link.springer.com/10.1007/BFb0051359, retrieved 2026-03-05
- ↑ 14.0 14.1 Cavell, R. G.; Day, E. D.; Byers, W.; Watkins, P. M. (December 1971). "Metal complexes of substituted dithiophosphinic acids. II. Complexes of trivalent vanadium" (in en). Inorganic Chemistry 10 (12): 2716–2719. doi:10.1021/ic50106a018. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50106a018.
- ↑ 15.0 15.1 15.2 15.3 15.4 Lustig, Max; Houk, Larry W. (November 1970). "Organometallic difluorodithiophosphates" (in en). Inorganic Chemistry 9 (11): 2462–2465. doi:10.1021/ic50093a016. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50093a016.
- ↑ Lustig, Max; Houk, Larry W. (October 1969). "A unidentate difluorodithiophosphate complex and a synthetic study of some dithio complexes" (in en). Inorganic and Nuclear Chemistry Letters 5 (10): 851–853. doi:10.1016/0020-1650(69)80071-1. https://linkinghub.elsevier.com/retrieve/pii/0020165069800711.
- ↑ 17.0 17.1 17.2 17.3 Cavell, R. G.; Sanger, A. R. (September 1972). "Metal complexes of substituted dithiophosphinic acids. VI. Reactions of difluorodithiophosphinic acid with chlorides and oxychlorides of chromium, molybdenum, and tungsten" (in en). Inorganic Chemistry 11 (9): 2011–2016. doi:10.1021/ic50115a005. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50115a005.
- ↑ 18.0 18.1 18.2 18.3 Hartman, Frederick A.; Lustig, Max (December 1968). "Preparation and reactions of tetracarbonyl-.mu.-bis(difluorodithiophosphato)-dirhodium(I)" (in en). Inorganic Chemistry 7 (12): 2669–2670. doi:10.1021/ic50070a051. ISSN 0020-1669. https://pubs.acs.org/doi/abs/10.1021/ic50070a051.
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