Difluorophosphate

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Difluorophosphate
Difluorophosphate ion.png
Ball-and-stick model of the difluorophosphate ion Difluorophosphate-3D-balls.png
Ball-and-stick model of the difluorophosphate ion
Spacefill model of difluorophosphate Difluorophosphate-3D-vdW.png
Spacefill model of difluorophosphate
Names
Systematic IUPAC name
Difluorophosphate [1]
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/F2HO2P/c1-5(2,3)4/h(H,3,4)/p-1
    Key: DGTVXEHQMSJRPE-UHFFFAOYSA-M
  • InChI=1/F2HO2P/c1-5(2,3)4/h(H,3,4)/p-1
    Key: DGTVXEHQMSJRPE-REWHXWOFAH
  • [O-]P(=O)(F)F
Properties
PO2F−2
Molar mass 100.97 g mol−1
Structure
Tetracoordinated at phosphorus atom
Tetrahedral at phosphorus atom
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula PO2F−2. It has a single negative charge and resembles perchlorate (ClO−4) and monofluorosulfonate (SO3F−) in shape and compounds. [2] These ions are isoelectronic, along with tetrafluoroaluminate, phosphate, orthosilicate, and sulfate. [2] [3] It forms a series of compounds. The ion is toxic to mammals as it causes blockage to iodine uptake in the thyroid. However it is degraded in the body over several hours. [2]

Compounds containing difluorophosphate may have it as a simple uninegative ion, it may function as a difluorophosphato ligand where it is covalently bound to one or two metal atoms, or go on to form a networked solid. [4] It may be covalently bound to a non metal or an organic moiety to make an ester or an amide.

Formation

Ammonium difluorophosphate ([NH4]PO2F2) is formed from treating phosphorus pentoxide with ammonium fluoride. [2] This was how the ion was first made by its discoverer, Willy Lange, in 1929. [3] [5] [ clarification needed ]

Alkali metal chlorides can react with dry difluorophosphoric acid to form alkali metal salts. [6]

NaCl + HPO2F2 → NaPO2F2 + HCl(g)

Fluorination of dichlorophosphates can produce difluorophosphates. [7] Another method is fluorination of phosphates or polyphosphates. [5] [ clarification needed ]

Trimethylsilyl difluorophosphate ((CH3)3Si−O−P(=O)F2) reacts with metal chlorides to give difluorophosphates. [8] [ clarification needed ]

The anhydride of difluorophosphoric acid (HPO2F2), phosphoryl difluoride oxide (P2O3F4) reacts with oxides such as UO3 to yield difuorophosphates. [9] Phosphoryl difluoride oxide also reacts with alkali metal fluorides to yield difluorophosphates. [10] [ clarification needed ]

Properties

The difluorophosphate ion in ammonium difluorophosphate and potassium difluorophosphate has these interatomic dimensions: [11]

Difluorophosphate saltP–O lengthP–F lengthO–P–O angleF–P–O angleF–P–F angle
Ammonium difluorophosphate1.457 Å 1.541 Å118.7°109.4°98.6°
Potassium difluorophosphate1.470 Å1.575 Å122.4°108.6°97.1°

Hydrogen bonding from ammonium ion to oxygen atoms causes a change to the difluorophosphate ion in the ammonium salt. [11]

On heating the salts that are not of alkali metals or alkaline earth metals, difluorophosphates decompose firstly by giving off POF3 forming a monofluorophosphate (PO3F2−) compound, and then this in turn decomposes to an orthophosphate PO3−4 compound. [12] [13]

Difluorophosphate salts are normally soluble and stable in water. However, in acidic or alkaline conditions they can be hydrolyzed to monofluorophosphates and hydrofluoric acid. [14] The caesium and potassium salts are the least soluble. [14]

Irradiating potassium difluorophosphate with gamma rays can make the free radicals •PO2F−, •PO3F− and •PO2F2. [15] [16] [ clarification needed ]

Compounds

FormulaNameStructureInfrared spectrumMelting pointCommentsReference
LiPO2F2Lithium difluorophosphate360 °C [5] [6]
Be(PO2F2)2Beryllium difluorophosphate>400 °C dprepared from BeCl2 and acid [17]
CH3CH2−O−P(=O)F2Ethyl difluorophosphate [18]
[NH4]+PO2F−2Ammonium difluorophosphateorthorhombic: a = 8.13 Å, b = 6.43 Å, c = 7·86 Å, Z = 4 space group PnmaP–F stretching 842 and 860 cm−1; P–O stretching 1138 and 1292 cm−1213 °C
[NO2]+PO2F−2Nitronium difluorophosphate515, 530, 550, 560, 575, 845, 880, 1145, 1300, 2390, 3760 cm−1 nitronium formed from anhydride and N2O5 [19]
[NO]+PO2F−2Nitrosonium difluorophosphate500, 840, 880, 1130, 1272, 1315, 2278 cm−1nitrosonium formed from anhydride and N2O3 [19]
NaPO2F2Sodium difluorophosphate210 °C [6]
Mg(PO2F2)2Magnesium difluorophosphate200 °C [5]
[NH4]+Mg2+(PO2F−2)3Ammonium magnesium difluorophosphateCmcm a=5.411 b=15.20 c=12.68 [20]
Al(PO2F2)3Aluminium difluorophosphatepolymeric [4] 505, 541, 582, 642, 918, 971, 1200, 1290 cm−1 (with 355 cm−1 impurity)formed from Al(CH2CH3)3 and acid; colourless insoluble powder [4] [7] [8]
Si(−O−P(=O)F2)4Silicon(IV) difluorophosphateformed from SiCl4 and anhydride [18]
(CH3)3Si−O−P(=O)F2Trimethylsilyl difluorophosphateformed from anhydride and [(CH3)3Si]2O [4] [18]
KPO2F2Potassium difluorophosphateorthorhombic: a = 8.03 Å, b = 6.205 Å, c = 7.633 Å, Z = 4, V=380.9 Å3, density = 2.44 g/cm3510, 525, 570, 835, 880, 1145, 1320, 1340 cm−1263 °Ccolourless elongated prisms [6] [11] [19] [21] [22]
(K+)4(PO2F−2)2(S2O2−7)Tetrapotassium difluorophosphate pyrosulfateC2/c: a = 13.00 Å, b = 7.543 Å, c = 19.01 Å, β = 130.07°, Z = 4 [23]
Ca(PO2F2)2· CH3COOCH2CH3 Calcium difluorophosphate - ethyl acetate 1:1 solvate [24]
Ca(PO2F2)2Calcium difluorophosphate>345 °C d [5]
[VO2]+PO2F−2Pervanadyl difluorophosphate [9]
CrO2(PO2F2)2Chromyl difluorophosphateformed from anhydride; red-brown [25]
Cr(PO2F2)3Chromium(III) difluorophosphate320, 385, 490, 575, 905, 955, 1165, 1255 cm−1formed from excess anhydride, green [25]
Mn(CO)5PO2F2[ clarification needed ]184 °C [26]
HMn(PO2F2)3[ clarification needed ]dissolve manganese in acid; white [27]
[NH+4](Mn2+)3(PO2F−2)(PO3F2−)2(F−)2 [28]
Fe(PO2F2)2Iron(II) difluorophosphate463, 496, 668 (weak), 869 (double), 1139, 1290 cm−1180 °C dcolour blue green, hygroscopic, melts 250 °C, above 300 °C starts decomposing to Fe3(PO4)2 [12]
Fe(PO2F2)3Iron(III) difluorophosphate262, 493, 528, 570, 914, 965, 1173, 1242 cm−1>400 °Cdecomposes at 230 °C yielding FeF3; dissolve iron in acid in presence of oxygen [7]
K+(Fe2+)3(PO2F−2)(PO3F2−)2(F−)2 [28]
Co(PO2F2)2Cobalt(II) difluorophosphate173 °Cprepared from CoCl2 and acid; pink or blue; blue formed by heating pink to 140 °C [17]
HCo(PO2F2)3[ clarification needed ]dissolve cobalt in acid; red-purple [27]
Co(PO2F2)2·2CH3CN Cobalt(II) difluorophosphate - methyl cyanide solvate 1:2orthorhombic: a = 9.227 Å, b = 13.871 Å, c = 9.471 Å, V = 1212 Å3, Z = 4, density = 1.88 g/cm3treat HCo(PO2F2)3 with CH3CN for a few weeks; red crystals [29]
[NH+4](Co2+)3(PO2F−2)(PO3F2−)2(F−)2 [28]
Ni(PO2F2)2Nickel(II) difluorophosphate255 °C dslowly prepared from NiCl2 and acid; yellow [17]
HNi(PO2F2)3[ clarification needed ]dissolve nickel in acid; yellow [27]
Cu(PO2F2)2Copper(II) difluorophosphateorthorhombic Fddd: a = 10.134 Å, b = 24.49 Å, c = 34.06 Å, Z = 48, V = 8454.3 Å3, density = 2.50 g/cm3265 °C dpale blue needles [5] [29]
CuI(xantphos)2(μ-PO2F2)polymeric; monoclinic: a = 12.435 Å, b = 10.887 Å, c = 25.682 Å, β = 100.220°, V = 3421 Å3colourless [30]
Zn(PO2F2)2Zinc(II) difluorophosphatec. 25 °C?glassy [5]
H2[Zn(PO2F2)4]Tetra(difluorophosphato)zincic(II) acid
Ga(PO2F2)3Gallium(III) difluorophosphate
[(CH3)2GaPO2F2]2Dimethylgallium(III) difluorophosphatedimeric380, 492, 520, 551, 616, 709, 750, 899, 949, 1171, 1218, 1262, 1295, 1404, 2922, 2982 cm−1 [4] [31]
RbPO2F2Rubidium difluorophosphateorthorhombic: a = 8.15 Å, b = 6.45 Å, c = 7.79 Å, Z = 4, V = 409.5 Å3 density = 3.02 g/cm3P–F stretching 827 and 946 cm−1; P–O stretching 1145 and 1320 cm−1160 °Cwhite [6] [11] [21]
Sr(PO2F2)2Strontium difluorophosphate250 °C dprepared from SrCl2 and acid [17]
[NH4]Sr(PO2F2)3Ammonium strontium difluorophosphateTriclinic P1a=7.370 b=11.054 c=13.645 α=88.861 β=87.435° γ=89.323° [20]
AgPO2F2Silver(I) difluorophosphate [32]
Ag9(PO2F2)14[ clarification needed ] [28]
Ag(1-methyl-2-alkylthiomethyl-1H-benzimidazole)PO2F2 [32]
Ag(2,6-bis-[(2-methylthiophenyl)-2-azaethenyl]pyridine)PO2F2Triclinic P1: a = 7.687 Å, b = 10.740 Å, c = 13.568 Å, α = 99.52°, β = 96.83°, γ = 99.83°, Z = 2, V = 1076 Å3, density = 1.81 g/cm3 [33]
Ag(4,4′-dicyano diphenylacetylene)PO2F2
Cd(PO2F2)2Cadmium(II) difluorophosphate245 °C d [5]
In(PO2F2)3Indium(III) difluorophosphate269, 492, 528, 567, 910, 962, 1179, 1269 cm−1white, decomposes at 260 °C yielding InF3 [7]
[(CH3)2InPO2F2]2Dimethylindium(III) difluorophosphatedimeric373, 490, 500, 535, 559, 735, 878, 925, 1128, 1179, 1275, 1435, 2928, 3000 cm−1 [31]
SnCl2(PO2F2)2Tin(IV) dichloride difluorophosphate [34]
(CH3)2Sn(PO2F2)2Dimethyltin(IV) difluorophosphate204 °C dprepared from (CH3)2SnCl2 and acid; yellow [17]
(CH3CH2)2Sn(PO2F2)2Diethyltin(IV) difluorophosphate262 °C dprepared from (CH3CH2)2SnCl2 and acid; yellow [17]
(CH3CH2CH2)2Sn(PO2F2)2Dipropyltin(IV) difluorophosphate245 °C dprepared from (CH3CH2CH2)2SnCl2 and acid; yellow [17]
(CH3(CH2)3)2Sn(PO2F2)2Dibutyltin(IV) difluorophosphate235 °C dprepared from (CH3(CH2)7)2SnCl2 and acid; yellow [17]
(CH3(CH2)7)2Sn(PO2F2)2Dioctyltin(IV) difluorophosphate114 °Cprepared from (CH3(CH2)7)2SnCl2 and acid; yellow [17]
SbCl4PO2F2Antimony(V) tetrachloride difluorophosphate [34]
SbF4PO2F2Antimony(V) tetrafluoride difluorophosphate [34]
(2,2-dipyradyl)2Re(CO)2PO2F2[ clarification needed ] [35]
Au[bis(triphenylphosphine sulfide-S)]PO2F2[ clarification needed ] [36]
IO2PO2F2[ clarification needed ] Raman: 130, 163, 191, 219, 295, 323, 329, 378, 637, 713, 737, 781, 799, 839, 918, 1163 cm−1yellowish colour, produced from IO3, decomposed by water [37]
IO3PO2F2[ clarification needed ] Raman: 217, 247, 269, 305, 343, 367, 395, 473, 569, 643, 671, 717, 797, 891, 1123 cm−1yellowish colour, produced from H5IO6, decomposed by water [37]
FXePO2F2Xenon(II) fluoride difluorophosphate [38]
Xe(PO2F2)2Xenon(II) difluorophosphate [38]
CsPO2F2Caesium difluorophosphateorthorhombic: a = 8.437 Å, b = 6.796 Å, c = 8.06 Å, Z = 4, V = 462.1 Å3, density = 3.36 g/cm3286 °C [6] [11] [21]
(Cs+)2(Fe3+)2(PO2F−2)(PO3F2−)2(F−)3 [28]
Ba(PO2F2)2Barium difluorophosphateorthorhombic I42d a =10.4935 b =10.4935 c =26.030>400 °C [5] [20]
[NH4]2Ba(PO2F2)4Diammonium barium difluorophosphateP2/n a=14.285 b=5.472 c=19.474 β=97.607° [20]
Re(CO)5PO2F2 [35]
Hg(PO2F2)2Mercury(II) difluorophosphate [5]
Hg2(PO2F2)2Mercury(I) difluorophosphate or di(difluorophosphato)dimercurane Raman: 220 cm−1produced from anhydride [5]
TlPO2F2Thallium(I) difluorophosphateproduced from anhydride, or acid on TlCl [5]
[(CH3)2TlPO2F2]2Dimethylthallium(III) difluorophosphatedimeric360, 374, 500, 505, 520, 559, 850, 880, 1120, 1140, 1195, 1250, 1285, 2932, 3020 cm−1 [31]
Pb(PO2F2)2Lead(II) difluorophosphate189 °C d [5]
UO2(PO2F2)2Uranyl difluorophosphate260, 498, 854, 924, 980, 1124 cm−1IR spectrum due to UO2+2 [9]
[(CH3CH2)4N]+PO2F−2Tetraethylammonium difluorophosphate [39]
1-ethyl-3-methylimidazolium difluorophosphateionic liquid [40]
1-butyl-3-methylimidazolium difluorophosphateionic liquid [40]
1-butyl-1-methylpyrrolidinium difluorophosphateionic liquid [40]
1-butyl-1-methylpiperidinium difluorophosphateionic liquid [40]
di(3,3′,4,4′-tetramethyl-2,2′,5,5′-tetraselenafulvalenium)difluorophosphateTransitions to a metallic state below 137 K (−136 °C) [41]
1,4-diphenyl-3,5-enanilo-4,5-dihydro-1,2,4-triazole (nitron)monoclinic P21/n: a = 7.3811 Å, b = 14.9963 Å, c = 16.922 Å, β = 102.138°, V = 1361.2 Å3, Z = 4insoluble; yellow-brown [2] [28]
Strychnine PO2F2 [3]
Cocaine PO2F2 [3]
Brucine PO2F2 [3]
Morphine PO2F2 [3]
[N(CH3)4]+PO2F−2Tetramethylammonium difluorophosphate [3]
H[B(PO2F2)4]Tetra(difluorophosphato)boric acid469, 502, 552, 647, 836, 940, 994, 1093, 1348, 1567 cm−1formed from BBr3 and acid; liquid [4]
Li[B(PO2F2)4]Lithium tetra(difluorophosphato)boratemonoclinic P21/c: a=7.9074 Å, b = 14.00602 Å, c = 13.7851 Å, β = 121.913°, Z = 4479, 502, 568, 833, 945, 1002, 1080, 1334 cm−1formed from HB(PO2F2)4 and butyllithium; colourless [4]
[HS(CH3)2]+[B(PO2F2)4]−Dimethylsulfonium tetra(difluorophosphato)borate472, 511, 555, 648, 832, 933, 993, 1082, 1337, 1436, 2851, 2921, 3042 cm−1formed from BH3 · S(CH3)2 and acid; ionic liquid [4]
[Li((CH3CH2)2O)+]3[Al(PO2F2)6]−(Diethyl ether)lithium hexa(difluorophosphato)aluminatetrigonal R3: a = 17.4058 Å, b = 17.4058 Å, c = 21.4947 Å, γ = 120°, Z = 6417, 503, 536, 624, 723, 891, 922, 964, 1174, 1204, 1283 cm−1formed from butyllithium and triethylaluminium and the acid; white [4]
K2CrO2(PO2F2)4305, 370, 485, 550, 870, 920, 1050, 1130, 1250 cm−1145 °C dformed from anhydride and K2CrO4; brown [25]
Na2MoO2(PO2F2)4amorphous280, 490, 620, 880, 915, 950, 1020, 1070, 1140, 1280 cm−1125 °C dformed from anhydride and K2MoO4; white [25]
Na2WO2(PO2F2)4amorphous280, 474, 620, 930, 1030, 1130, 1230 cm−1109 °C dformed from anhydride and K2WO4; white [25]

Difluorphosphoric acid

Difluorophosphoric acid (HPO2F2) is one of the fluorophosphoric acids. It is produced when phosphoryl fluoride reacts with water:

POF3 + H2O → HPO2F2 + HF

This in turn is hydrolysed more to give monofluorophosphoric acid (H2PO3F), and a trace of hexafluorophosphoric acid (HPF6). HPO2F2 also is produced when HF reacts with phosphorus pentoxide. Yet another method involves making difluorphosphoric acid as a side product of calcium fluoride being heated with damp phosphorus pentoxide. A method to make pure difluorphosphoric acid involves heating phosphoryl fluoride with monofluorophosphoric acid and separating the product by distillation: [42]

POF3 + H2PO3F → 2 HPO2F2

Difluorophosphoric acid can also be produced by fluorinating phosphorus oxychlorides. P2O3Cl4 and POCl3 react with hydrogen fluoride solution to yield HPO2Cl2 and then HPO2F2. [43] Yet another way is to treat orthophosphate (PO3−4) with fluorosulfuric acid (HSO3F). [44]

Difluorphosphoric acid is a colorless liquid. It melts at −96.5 °C (−141.7 °F) and boils at 115.9 °C (240.6 °F). Its density at 25 °C is 1.583 g/cm3. [14]

Phosphoryl difluoride oxide

Difluorophosphoric acid anhydride also known as phosphoryl difluoride oxide or diphosphoryl tetrafluoride (F2(O=)P−O−P(=O)F2 or P2O3F4) is an anhydride of difluorphosphoric acid. It crystallises in the orthorhombic system, with space group Pcca and Z = 4. [45] P2O3F4 can be made by refluxing difluorophosphoric acid with phosphorus pentoxide. P2O3F4 boils at 71 °C. [46]

Substitution

In addition to the isoelectronic series, ions related by substituting fluorine or oxygen by other elements include monofluorophosphate, difluorothiophosphate, dichlorothiophosphate, dichlorophosphate, chlorofluorothiophosphate, chlorofluorophosphate, dibromophosphate, and bromofluorophosphate. [47]

Adducts

Difluorophosphate can form adducts with PF5 and AsF5 . In these the oxygen atoms form a donor-acceptor link between the P and As (or P) atoms, linking the difluorides to the pentafluorides. Example salts include KPO2F2·2AsF5, KPO2F2·AsF5, KPO2F2·2PF5 and KPO2F2·PF5. [48]

Amines can react with phosphoryl fluoride to make substances with a formula RR′N−P(=O)F2. The amines shown to do this include ethylamine, isopropylamine, n-butylamine, t-butylamine, dimethylamine, and diethylamine. The monoamines can further react to yield an alkyliminophosphoric fluoride (R−N=P(=O)F). [49]

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1,3-Difluoro-trisulfane-1,1-difluoride is an inorganic molecular substance with the structure SF3SSF, consisting of sulfur in a low oxidation state with fluorine. The compound consists of a chain of three sulfur atoms, with three fluorine atoms bonded to the sulfur on one end and the fourth fluorine bonded to the sulfur on the other end. It has a melting point of -62 °C and a boiling point of 94 °C. As a gas, it is unstable and breaks up to form SSF2 and SF4.

<span class="mw-page-title-main">Difluorophosphoric acid</span> Chemical compound

Difluorophosphoric acid is an inorganic compound with the formula HPO2F2. It is a mobile colorless strongly fuming liquid. The acid has limited applications, in part because it is thermally and hydrolytically unstable. Difluorophosphoric acid is corrosive to glass, fabric, metals and living tissue.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

Nitride fluorides containing nitride and fluoride ions with the formula NF4-. They can be electronically equivalent to a pair of oxide ions O24-. Nitride fluorides were discovered in 1996 by Lavalle et al. They heated diammonium technetium hexafluoride to 300 °C to yield TcNF. Another preparation is to heat a fluoride compound with a nitride compound in a solid state reaction. The fluorimido ion is F-N2- and is found in a rhenium compound.

<span class="mw-page-title-main">Hexafluoroarsenate</span> Chemical compound

The hexafluoroarsenate anion is a chemical species with formula AsF−6. Hexafluoroarsenate is relatively inert, being the conjugate base of the notional superacid hexafluoroarsenic acid.

References

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