Chemistry:Difluorophosphate

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Difluorophosphate
Structure of difluorophosphate ion
Ball-and-stick model of the difluorophosphate ion
Spacefill model of difluorophosphate
Names
Systematic IUPAC name
Difluorophosphate[1]
Identifiers
3D model (JSmol)
ChemSpider
Properties
PO
2F−
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).
☒N (what is ☑Y☒N ?)
Infobox references
Tracking categories (test):

Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula PO
2F−
2. It has a single negative charge and resembles perchlorate (ClO−
4) and monofluorosulfonate (SO
3F−
) 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 ([NH
4]PO
2F
2) 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 + HPO
2F
2 → NaPO
2F
2 + HCl(g)

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

Trimethylsilyl difluorophosphate ((CH
3)
3Si–O–P(=O)F
2) reacts with metal chlorides to give difluorophosphates.[8][clarification needed]

The anhydride of difluorophosphoric acid (HPO
2F
2), phosphoryl difluoride oxide (P
2O
3F
4) reacts with oxides such as UO
3 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 salt P–O length P–F length O–P–O angle F–P–O angle F–P–F angle
Ammonium difluorophosphate 1.457 Å 1.541 Å 118.7° 109.4° 98.6°
Potassium difluorophosphate 1.470 Å 1.575 Å 122.4° 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 POF
3 forming a monofluorophosphate (PO
3F2−) 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 •PO
2F−
, •PO
3F−
 and •PO
2F
2.[15][16][clarification needed]

Compounds

Formula Name Structure Infrared spectrum Melting point Comments Reference
LiPO
2F
2 		Lithium difluorophosphate 360 °C [5][6]
Be(PO
2F
2)
2 		Beryllium difluorophosphate >400 °C d prepared from BeCl
2 and acid 		[17]
CH
3CH
2–O–P(=O)F
2 		Ethyl difluorophosphate [18]
[NH
4]+
PO
2F−
2 		Ammonium difluorophosphate orthorhombic: a = 8.13 Å, b = 6.43 Å, c = 7·86 Å, Z = 4 space group Pnma P–F stretching 842 and 860 cm−1; P–O stretching 1138 and 1292 cm−1 213 °C
[NO
2]+
PO
2F−
2 		Nitronium difluorophosphate 515, 530, 550, 560, 575, 845, 880, 1145, 1300, 2390, 3760 cm−1 nitronium formed from anhydride and N
2O
5 		[19]
[NO]+
PO
2F−
2 		Nitrosonium difluorophosphate 500, 840, 880, 1130, 1272, 1315, 2278 cm−1 nitrosonium formed from anhydride and N
2O
3 		[19]
NaPO
2F
2 		Sodium difluorophosphate 210 °C [6]
Mg(PO
2F
2)
2 		Magnesium difluorophosphate 200 °C [5]
[NH
4]+
Mg2+(PO
2F−
2)
3 		Ammonium magnesium difluorophosphate Cmcm a=5.411 b=15.20 c=12.68 [20]
Al(PO
2F
2)
3 		Aluminium difluorophosphate polymeric[4] 505, 541, 582, 642, 918, 971, 1200, 1290 cm−1 (with 355 cm−1 impurity) formed from Al(CH
2CH
3)
3 and acid; colourless insoluble powder[4] 		[7][8]
Si(–O–P(=O)F
2)
4 		Silicon(IV) difluorophosphate formed from SiCl
4 and anhydride 		[18]
(CH
3)
3Si–O–P(=O)F
2 		Trimethylsilyl difluorophosphate formed from anhydride and [(CH
3)
3Si]
2O 		[4][18]
KPO
2F
2 		Potassium difluorophosphate orthorhombic: a = 8.03 Å, b = 6.205 Å, c = 7.633 Å, Z = 4, V=380.9 Å3, density = 2.44 g/cm3 510, 525, 570, 835, 880, 1145, 1320, 1340 cm−1 263 °C colourless elongated prisms [6][11][19][21][22]
(K+
)
4(PO
2F−
2)
2(S
2O2−
7) 		Tetrapotassium difluorophosphate pyrosulfate C2/c: a = 13.00 Å, b = 7.543 Å, c = 19.01 Å, β = 130.07°, Z = 4 [23]
Ca(PO
2F
2)
2 · CH
3COOCH
2CH
3 		Calcium difluorophosphate - ethyl acetate 1:1 solvate [24]
Ca(PO
2F
2)
2 		Calcium difluorophosphate >345 °C d [5]
[VO
2]+
PO
2F−
2 		Pervanadyl difluorophosphate [9]
CrO
2(PO
2F
2)
2 		Chromyl difluorophosphate formed from anhydride; red-brown [25]
Cr(PO
2F
2)
3 		Chromium(III) difluorophosphate 320, 385, 490, 575, 905, 955, 1165, 1255 cm−1 formed from excess anhydride, green [25]
Mn(CO)
5PO
2F
2[clarification needed] 		184 °C [26]
HMn(PO
2F
2)
3[clarification needed] 		dissolve manganese in acid; white [27]
[NH+
4](Mn2+)
3(PO
2F−
2)(PO
3F2−)
2(F−
)
2 		[28]
Fe(PO
2F
2)
2 		Iron(II) difluorophosphate 463, 496, 668 (weak), 869 (double), 1139, 1290 cm−1 180 °C d colour blue green, hygroscopic, melts 250 °C, above 300 °C starts decomposing to Fe
3(PO
4)
2 		[12]
Fe(PO
2F
2)
3 		Iron(III) difluorophosphate 262, 493, 528, 570, 914, 965, 1173, 1242 cm−1 >400 °C decomposes at 230 °C yielding FeF
3; dissolve iron in acid in presence of oxygen 		[7]
K+
(Fe2+)
3(PO
2F−
2)(PO
3F2−)
2(F−
)
2 		[28]
Co(PO
2F
2)
2 		Cobalt(II) difluorophosphate 173 °C prepared from CoCl
2 and acid; pink or blue; blue formed by heating pink to 140 °C 		[17]
HCo(PO
2F
2)
3[clarification needed] 		dissolve cobalt in acid; red-purple [27]
Co(PO
2F
2)
2 · 2CH
3CN 		Cobalt(II) difluorophosphate - methyl cyanide solvate 1:2 orthorhombic: a = 9.227 Å, b = 13.871 Å, c = 9.471 Å, V = 1212 Å3, Z = 4, density = 1.88 g/cm3 treat HCo(PO
2F
2)
3 with CH
3CN for a few weeks; red crystals 		[29]
[NH+
4](Co2+)
3(PO
2F−
2)(PO
3F2−)
2(F−
)
2 		[28]
Ni(PO
2F
2)
2 		Nickel(II) difluorophosphate 255 °C d slowly prepared from NiCl
2 and acid; yellow 		[17]
HNi(PO
2F
2)
3[clarification needed] 		dissolve nickel in acid; yellow [27]
Cu(PO
2F
2)
2 		Copper(II) difluorophosphate orthorhombic Fddd: a = 10.134 Å, b = 24.49 Å, c = 34.06 Å, Z = 48, V = 8454.3 Å3, density = 2.50 g/cm3 265 °C d pale blue needles [5][29]
CuI(xantphos)
2(μ-PO
2F
2) 		polymeric; monoclinic: a = 12.435 Å, b = 10.887 Å, c = 25.682 Å, β = 100.220°, V = 3421 Å3 colourless [30]
Zn(PO
2F
2)
2 		Zinc(II) difluorophosphate c. 25 °C? glassy [5]
H
2[Zn(PO
2F
2)
4] 		Tetra(difluorophosphato)zincic(II) acid
Ga(PO
2F
2)
3 		Gallium(III) difluorophosphate
[(CH
3)
2GaPO
2F
2]
2 		Dimethylgallium(III) difluorophosphate dimeric 380, 492, 520, 551, 616, 709, 750, 899, 949, 1171, 1218, 1262, 1295, 1404, 2922, 2982 cm−1 [4][31]
RbPO
2F
2 		Rubidium difluorophosphate orthorhombic: a = 8.15 Å, b = 6.45 Å, c = 7.79 Å, Z = 4, V = 409.5 Å3 density = 3.02 g/cm3 P–F stretching 827 and 946 cm−1; P–O stretching 1145 and 1320 cm−1 160 °C white [6][11][21]
Sr(PO
2F
2)
2 		Strontium difluorophosphate 250 °C d prepared from SrCl
2 and acid 		[17]
[NH
4]Sr(PO
2F
2)
3 		Ammonium strontium difluorophosphate Triclinic P1 a=7.370 b=11.054 c=13.645 α=88.861 β=87.435° γ=89.323° [20]
AgPO
2F
2 		Silver(I) difluorophosphate [32]
Ag
9(PO
2F
2)
14[clarification needed] 		[28]
Ag(1-methyl-2-alkylthiomethyl-1H-benzimidazole)PO
2F
2 		[32]
Ag(2,6-bis-[(2-methylthiophenyl)-2-azaethenyl]pyridine)PO
2F
2 		Triclinic 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′-dicyanodiphenylacetylene)PO
2F
2
Cd(PO
2F
2)
2 		Cadmium(II) difluorophosphate 245 °C d [5]
In(PO
2F
2)
3 		Indium(III) difluorophosphate 269, 492, 528, 567, 910, 962, 1179, 1269 cm−1 white, decomposes at 260 °C yielding InF
3 		[7]
[(CH
3)
2InPO
2F
2]
2 		Dimethylindium(III) difluorophosphate dimeric 373, 490, 500, 535, 559, 735, 878, 925, 1128, 1179, 1275, 1435, 2928, 3000 cm−1 [31]
SnCl
2(PO
2F
2)
2 		Tin(IV) dichloride difluorophosphate [34]
(CH
3)
2Sn(PO
2F
2)
2 		Dimethyltin(IV) difluorophosphate 204 °C d prepared from (CH
3)
2SnCl
2 and acid; yellow 		[17]
(CH
3CH
2)
2Sn(PO
2F
2)
2 		Diethyltin(IV) difluorophosphate 262 °C d prepared from (CH
3CH
2)
2SnCl
2 and acid; yellow 		[17]
(CH
3CH
2CH
2)
2Sn(PO
2F
2)
2 		Dipropyltin(IV) difluorophosphate 245 °C d prepared from (CH
3CH
2CH
2)
2SnCl
2 and acid; yellow 		[17]
(CH
3(CH
2)
3)
2Sn(PO
2F
2)
2 		Dibutyltin(IV) difluorophosphate 235 °C d prepared from (CH
3(CH
2)
7)
2SnCl
2 and acid; yellow 		[17]
(CH
3(CH
2)
7)
2Sn(PO
2F
2)
2 		Dioctyltin(IV) difluorophosphate 114 °C prepared from (CH
3(CH
2)
7)
2SnCl
2 and acid; yellow 		[17]
SbCl
4PO
2F
2 		Antimony(V) tetrachloride difluorophosphate [34]
SbF
4PO
2F
2 		Antimony(V) tetrafluoride difluorophosphate [34]
(2,2-dipyradyl)2Re(CO)
2PO
2F
2[clarification needed] 		[35]
Au[bis(triphenylphosphine sulfide-S)]PO
2F
2[clarification needed] 		[36]
IO
2PO
2F
2[clarification needed] 		Raman: 130, 163, 191, 219, 295, 323, 329, 378, 637, 713, 737, 781, 799, 839, 918, 1163 cm−1 yellowish colour, produced from IO
3, decomposed by water 		[37]
IO
3PO
2F
2[clarification needed] 		Raman: 217, 247, 269, 305, 343, 367, 395, 473, 569, 643, 671, 717, 797, 891, 1123 cm−1 yellowish colour, produced from H
5IO
6, decomposed by water 		[37]
FXePO
2F
2 		Xenon(II) fluoride difluorophosphate [38]
Xe(PO
2F
2)
2 		Xenon(II) difluorophosphate [38]
CsPO
2F
2 		Caesium difluorophosphate orthorhombic: a = 8.437 Å, b = 6.796 Å, c = 8.06 Å, Z = 4, V = 462.1 Å3, density = 3.36 g/cm3 286 °C [6][11][21]
(Cs+
)
2(Fe3+)
2(PO
2F−
2)(PO
3F2−)
2(F−
)
3 		[28]
Ba(PO
2F
2)
2 		Barium difluorophosphate orthorhombic I42d a =10.4935 b =10.4935 c =26.030 >400 °C [5][20]
[NH
4]
2Ba(PO
2F
2)
4 		Diammonium barium difluorophosphate P2/n a=14.285 b=5.472 c=19.474 β=97.607° [20]
Re(CO)
5PO
2F
2 		[35]
Hg(PO
2F
2)
2 		Mercury(II) difluorophosphate [5]
Hg
2(PO
2F
2)
2 		Mercury(I) difluorophosphate or di(difluorophosphato)dimercurane Raman: 220 cm−1 produced from anhydride [5]
TlPO
2F
2 		Thallium(I) difluorophosphate produced from anhydride, or acid on TlCl [5]
[(CH
3)
2TlPO
2F
2]
2 		Dimethylthallium(III) difluorophosphate dimeric 360, 374, 500, 505, 520, 559, 850, 880, 1120, 1140, 1195, 1250, 1285, 2932, 3020 cm−1 [31]
Pb(PO
2F
2)
2 		Lead(II) difluorophosphate 189 °C d [5]
UO
2(PO
2F
2)
2 		Uranyl difluorophosphate 260, 498, 854, 924, 980, 1124 cm−1 IR spectrum due to UO2+
2 		[9]
[(CH
3CH
2)
4N]+
PO
2F−
2 		Tetraethylammonium difluorophosphate [39]
1-ethyl-3-methylimidazolium difluorophosphate ionic liquid [40]
1-butyl-3-methylimidazolium difluorophosphate ionic liquid [40]
1-butyl-1-methylpyrrolidinium difluorophosphate ionic liquid [40]
1-butyl-1-methylpiperidinium difluorophosphate ionic liquid [40]
di(3,3′,4,4′-tetramethyl-2,2′,5,5′-tetraselenafulvalenium)difluorophosphate Transitions 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 = 4 insoluble; yellow-brown [2][28]
Strychnine PO
2F
2 		[3]
Cocaine PO
2F
2 		[3]
Brucine PO
2F
2 		[3]
Morphine PO
2F
2 		[3]
[N(CH
3)
4]+
PO
2F−
2 		Tetramethylammonium difluorophosphate [3]
H[B(PO
2F
2)
4] 		Tetra(difluorophosphato)boric acid 469, 502, 552, 647, 836, 940, 994, 1093, 1348, 1567 cm−1 formed from BBr
3 and acid; liquid 		[4]
Li[B(PO
2F
2)
4] 		Lithium tetra(difluorophosphato)borate monoclinic P21/c: a=7.9074 Å, b = 14.00602 Å, c = 13.7851 Å, β = 121.913°, Z = 4 479, 502, 568, 833, 945, 1002, 1080, 1334 cm−1 formed from HB(PO
2F
2)
4 and butyllithium; colourless 		[4]
[HS(CH
3)
2]+
[B(PO
2F
2)
4]−
 		Dimethylsulfonium tetra(difluorophosphato)borate 472, 511, 555, 648, 832, 933, 993, 1082, 1337, 1436, 2851, 2921, 3042 cm−1 formed from BH
3 · S(CH
3)
2 and acid; ionic liquid 		[4]
[Li((CH
3CH
2)
2O)+
]
3[Al(PO
2F
2)
6]−
 		(Diethyl ether)lithium hexa(difluorophosphato)aluminate trigonal R3: a = 17.4058 Å, b = 17.4058 Å, c = 21.4947 Å, γ = 120°, Z = 6 417, 503, 536, 624, 723, 891, 922, 964, 1174, 1204, 1283 cm−1 formed from butyllithium and triethylaluminium and the acid; white [4]
K
2CrO
2(PO
2F
2)
4 		305, 370, 485, 550, 870, 920, 1050, 1130, 1250 cm−1 145 °C d formed from anhydride and K
2CrO
4; brown 		[25]
Na
2MoO
2(PO
2F
2)
4 		amorphous 280, 490, 620, 880, 915, 950, 1020, 1070, 1140, 1280 cm−1 125 °C d formed from anhydride and K
2MoO
4; white 		[25]
Na
2WO
2(PO
2F
2)
4 		amorphous 280, 474, 620, 930, 1030, 1130, 1230 cm−1 109 °C d formed from anhydride and K
2WO
4; white 		[25]

Related substances

Difluorphosphoric acid

Difluorophosphoric acid (HPO
2F
2) is one of the fluorophosphoric acids. It is produced when phosphoryl fluoride reacts with water:

POF
3 + H
2O → HPO
2F
2 + HF

This in turn is hydrolysed more to give monofluorophosphoric acid (H
2PO
3F), and a trace of hexafluorophosphoric acid (HPF
6). HPO
2F
2 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]

POF
3 + H
2PO
3F → 2 HPO
2F
2

Difluorophosphoric acid can also be produced by fluorinating phosphorus oxychlorides. P
2O
3Cl
4 and POCl
3 react with hydrogen fluoride solution to yield HPO
2Cl
2 and then HPO
2F
2.[43] Yet another way is to treat orthophosphate (PO3−
4) with fluorosulfuric acid (HSO
3F).[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 (F
2(O=)P–O–P(=O)F
2 or P
2O
3F
4) is an anhydride of difluorphosphoric acid. It crystallises in the orthorhombic system, with space group Pcca and Z = 4.[45] P
2O
3F
4 can be made by refluxing difluorophosphoric acid with phosphorus pentoxide. P
2O
3F
4 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 PF
5 and AsF
5. 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 KPO
2F
2 · 2AsF
5, KPO
2F
2 · AsF
5, KPO
2F
2 · 2PF
5 and KPO
2F
2 · PF
5.[48]

Amines can react with phosphoryl fluoride to make substances with a formula RR′N–P(=O)F
2. 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]

References

  1. ↑ Toy, Arthur D. F. (22 Oct 2013). The Chemistry of Phosphorus. Pergamon Texts in Inorganic Chemistry. 3. Pergamon Press. pp. 536–537. ISBN 9781483147413. https://books.google.com/books?id=4Ub9BAAAQBAJ&pg=PA536. Retrieved 19 June 2015. 
  2. ↑ 2.0 2.1 2.2 2.3 2.4 Anbar, M.; Guttmann, S.; Lewitus, Z. (30 May 1959). "Effect of Monofluorosulphonate, Difluorophosphate and Fluoroborate Ions on the Iodine Uptake of the Thyroid Gland". Nature 183 (4674): 1517–1518. doi:10.1038/1831517a0. PMID 13666792. Bibcode: 1959Natur.183.1517A. 
  3. ↑ 3.0 3.1 3.2 3.3 3.4 3.5 3.6 Lange, Willy (3 April 1929). "Über die Difluorphosphorsäure und ihre der Perchlorsäure ähnliche Salzbildung". Berichte der Deutschen Chemischen Gesellschaft (A and B Series) 62 (4): 786–792. doi:10.1002/cber.19290620408. 
  4. ↑ 4.0 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 Schulz, Christoph; Eiden, Philipp; Klose, Petra; Ermantraut, Andreas; Schmidt, Michael; Garsuch, Arnd; Krossing, Ingo (2015). "Homoleptic borates and aluminates containing the difluorophosphato ligand – [M(O2PF2)x]y− – synthesis and characterization". Dalton Trans. 44 (15): 7048–7057. doi:10.1039/c5dt00469a. PMID 25785817. 
  5. ↑ 5.00 5.01 5.02 5.03 5.04 5.05 5.06 5.07 5.08 5.09 5.10 5.11 5.12 Vast, P.; Semmoud, A.; Addou, A.; Palavit, G. (March 1988). "Étude méthodologique de la synthèse des difluorodioxophosphates métalliques à partir de l'oxyde difluorure de phosphoryle". Journal of Fluorine Chemistry 38 (3): 297–302. doi:10.1016/S0022-1139(00)81065-9. 
  6. ↑ 6.0 6.1 6.2 6.3 6.4 6.5 Thompson, R.C.; Reed, W. (July 1969). "Preparation and infrared spectra of alkali metal difluorophosphates". Inorganic and Nuclear Chemistry Letters 5 (7): 581–585. doi:10.1016/0020-1650(69)80034-6. 
  7. ↑ 7.0 7.1 7.2 7.3 Weidlein, J. (April 1968). "Darstellung, Eigenschaften und IR-Spektren von OTi(O2PCl2)2, Fe(O2PF2)3 und In(O2PF2)3". Zeitschrift für anorganische und allgemeine Chemie 358 (1–2): 13–20. doi:10.1002/zaac.19683580103. 
  8. ↑ 8.0 8.1 Shihada, Abdel-Fattah; Mohammed, Abdulalah T. (1 January 1980). "Zur Reaktion von Trimethylsilyl-difluorophosphat, Trimethylsilyl-dimethylphosphinat und Difluorophosphorsäureanhydrid mit TiCl4 bzw. SbCl5". Zeitschrift für Naturforschung B 35 (1): 60–63. doi:10.1515/znb-1980-0114. 
  9. ↑ 9.0 9.1 9.2 Vast, P.; Semmoud, A. (January 1985). "Préparation de nouveaux difluorodioxophosphates à partir de l'oxyde de difluorure de phosphoryle. Partie V. Réactions sur le trioxyde d'uranium". Journal of Fluorine Chemistry 27 (1): 47–52. doi:10.1016/S0022-1139(00)80896-9. 
  10. ↑ Addou, A.; Vast, P.; Legrand, P. (January 1982). "Champ de forces de symetrie locale des composés oxyfluorés du phosphore(V). I. Les difluorodioxophosphates (DFP) alcalins". Spectrochimica Acta Part A: Molecular Spectroscopy 38 (7): 785–790. doi:10.1016/0584-8539(82)80068-8. Bibcode: 1982AcSpA..38..785A. 
  11. ↑ 11.0 11.1 11.2 11.3 11.4 Harrison, R. W.; Trotter, James (1969). "Structure of ammonium difluorophosphate". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1783. doi:10.1039/J19690001783. 
  12. ↑ 12.0 12.1 Vast, P.; Semmoud, A. (June 1994). "Comportement thermique du difluorodioxophosphate ferreux". Journal of Thermal Analysis 41 (6): 1489–1493. doi:10.1007/bf02549945. 
  13. ↑ Vast, P.; Semmoud, A.; Palavit, G. (December 1986). "Préparation de l'acide monofluorotrioxophosphorique H2PO3F à partir de l'acide difluorodioxophosphorique HPO2F2". Journal of Fluorine Chemistry 34 (2): 229–232. doi:10.1016/s0022-1139(00)85072-1. 
  14. ↑ 14.0 14.1 14.2 Reed, William (September 1965). Studies of Difluorophosphoric Acid and its Alkali Metal Salts (Thesis). Retrieved 23 April 2023.
  15. ↑ Begum, Afrozi; Subramanian, S.; Symons, M. C. R. (1970). "Unstable intermediates. Part LXVIII. Electron spin resonance studies of the radicals O3PF− and O2PF2". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1323. doi:10.1039/J19700001323. 
  16. ↑ Begum, A.; Subramanian, S.; Symons, M. C. R. (1971). "Unstable intermediates. Part LXXXVI. Electron spin resonance studies of the effect of γ-rays on potassium difluorophosphate: the radical PO2F?". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 700–702. doi:10.1039/J19710000700. 
  17. ↑ 17.0 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 Tan, Thiam Hock (August 1970). Preparation and Properties of Metal Difluorophosphates (Thesis). University of British Columbia. Archived from the original (PDF) on 2016-03-04.
  18. ↑ 18.0 18.1 18.2 Roesky, Herbert W. (July 1967). "Über Reaktionen mit Pyrophosphoryltetrafluorid". Chemische Berichte 100 (7): 2147–2150. doi:10.1002/cber.19671000706. 
  19. ↑ 19.0 19.1 19.2 Addou, A.; Vast, P. (August 1979). "Préparation de nouveaux difluorodioxophosphates à partir de l'oxyde de difluororure de phosphoryle. Partie I. Réactions sur les oxydes d'azote". Journal of Fluorine Chemistry 14 (2): 163–169. doi:10.1016/S0022-1139(00)82884-5. 
  20. ↑ 20.0 20.1 20.2 20.3 Zhang, Wenyao; Jin, Wenqi; Cheng, Meng; Zhang, Ruonan; Yang, Zhihua; Pan, Shilie (2021). "From centrosymmetric to noncentrosymmetric: effect of the cation on the crystal structures and birefringence values of (NH 4 ) n−2 AE(PO 2 F 2 ) n (AE = Mg, Sr and Ba; n = 2, 3 and 4)" (in en). Dalton Transactions 50 (29): 10206–10213. doi:10.1039/D1DT00698C. ISSN 1477-9226. PMID 34231608. http://xlink.rsc.org/?DOI=D1DT00698C. 
  21. ↑ 21.0 21.1 21.2 Trotter, James; Whitlow, S. H. (1967). "The structures of caesium and rubidium difluorophosphates". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1383–1386. doi:10.1039/J19670001383. 
  22. ↑ Harrison, R. W.; Thompson, R. C.; Trotter, James (1966). "The structure of potassium difluorophosphate". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1775. doi:10.1039/J19660001775. 
  23. ↑ Zhang, Wenyao; Jin, Wenqi; Yang, Zhihua; Pan, Shilie (2020). "K4(PO2F2)2(S2O7): first fluorooxophosphorsulfate with mixed-anion [S2O72− and [PO2F2]− groups"] (in en). Dalton Transactions 49 (48): 17658–17664. doi:10.1039/D0DT03307C. ISSN 1477-9226. PMID 33231582. http://xlink.rsc.org/?DOI=D0DT03307C. 
  24. ↑ Grunze, H.; Jost, K.-H.; Wolf, G.-U. (April 1969). "Salze von Halogenophosphorsäuren. V. Darstellung und Struktur des Bis(äthylacetat)-calcium-difluorophosphates Ca[PO2F2]2 · 2 CH3COOC2H5". Zeitschrift für anorganische und allgemeine Chemie 365 (5–6): 294–300. doi:10.1002/zaac.19693650509. 
  25. ↑ 25.0 25.1 25.2 25.3 25.4 Brown, S.D.; Emme, L.M.; Gard, G.L. (December 1975). "The reaction of chromium trioxide and metal oxide salts with P2O3F4". Journal of Inorganic and Nuclear Chemistry 37 (12): 2557–2558. doi:10.1016/0022-1902(75)80891-8. 
  26. ↑ Wimmer, F.L.; Snow, M.R. (1978). "Perchlorate and difluorophosphate coordination derivatives of manganese carbonyl". Australian Journal of Chemistry 31 (2): 267. doi:10.1071/CH9780267. 
  27. ↑ 27.0 27.1 27.2 Dove, Michael F. A.; Hibbert, Richard C.; Logan, Norman (1985). "Difluorophosphate complexes of chromium, manganese, iron, cobalt, and nickel". Journal of the Chemical Society, Dalton Transactions (4): 707. doi:10.1039/DT9850000707. 
  28. ↑ 28.0 28.1 28.2 28.3 28.4 28.5 Weil, Matthias; Fürst, Markus (2020-07-01). "Crystal structure of (1,4-diphenyl-4H-1,2,4-triazol-3-yl)phenylamine difluorophosphate, and a survey of the difluorophosphate anion (PO2F2−)". Acta Crystallographica Section E 76 (7): 1003–1006. doi:10.1107/S2056989020006933. ISSN 2056-9890. PMID 32695441. 
  29. ↑ 29.0 29.1 Begley, Michael J.; Dove, Michael F. A.; Hibbert, Richard C.; Logan, Norman; Nunn, Michael; Sowerby, D. Bryan (1985). "Crystal structures of the difluorophosphate complexes, Co(O2PF2)2 · 2MeCN and Cu(O2PF2)2". Journal of the Chemical Society, Dalton Transactions (11): 2433–2436. doi:10.1039/DT9850002433. 
  30. ↑ Keller, Sarah; Brunner, Fabian; Prescimone, Alessandro; Constable, Edwin C.; Housecroft, Catherine E. (August 2015). "Hexafluoridophosphate partial hydrolysis leading to the one-dimensional coordination polymer [{Cu(xantphos)(μ-PO2F2)}n]". Inorganic Chemistry Communications 58: 64–66. doi:10.1016/j.inoche.2015.06.002. 
  31. ↑ 31.0 31.1 31.2 Schaible, B.; Weidlein, J. (February 1974). "Untersuchungen an Dialkylmetallphosphor- und -phosphinsäurederivaten der Elemente Aluminium, Gallium, Indium und Thallium. II. Die Schwingungsspektren der Difluoro- und Dichlorophosphate". Zeitschrift für anorganische und allgemeine Chemie 403 (3): 301–309. doi:10.1002/zaac.19744030309. 
  32. ↑ 32.0 32.1 Albrecht, Markus; Hübler, Klaus; Kaim, Wolfgang (May 2000). "Syntheses, Structures, and Properties of the Complexes [Ag(N∧S)n](X), N∧S = 1-Methyl-2-(alkylthiomethyl)-1H-benzimidazoles, X = PF6 (n = 2) or PO2F2 (n = 1)". Zeitschrift für anorganische und allgemeine Chemie 626 (5): 1033–1037. doi:10.1002/(SICI)1521-3749(200005)626:5<1033::AID-ZAAC1033>3.0.CO;2-A. 
  33. ↑ Fessler, Th. U.; Hübener, R.; Strähle, J. (September 1997). "Synthese von Kupfer- und Silberkomplexen mit fünfzähnigen N,S- und sechszähnigen N,O-Chelatliganden – Charakterisierung und Kristallstrukturen von {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2 und {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2". Zeitschrift für anorganische und allgemeine Chemie 623 (9): 1367–1374. doi:10.1002/zaac.19976230908. 
  34. ↑ 34.0 34.1 34.2 Krüger, N.; Dehnicke, K.; Shihada, A.-F. (February 1978). "Difluorophosphate von Zinn(IV) und Antimon(V)". Zeitschrift für anorganische und allgemeine Chemie 438 (1): 169–175. doi:10.1002/zaac.19784380118. 
  35. ↑ 35.0 35.1 Horn, E.; Snow, M.R. (1980). "Perchlorate and difluorophosphate coordination derivatives of rhenium carbonyl". Australian Journal of Chemistry 33 (11): 2369. doi:10.1071/CH9802369. 
  36. ↑ LeBlanc, D. J.; Britten, J. F.; Lock, C. J. L. (15 September 1997). "Bis(triphenylphosphine sulfide-)gold(I) Difluorophosphate(V)". Acta Crystallographica Section C 53 (9): 1204–1206. doi:10.1107/S0108270197005209. 
  37. ↑ 37.0 37.1 Addou, A.; Vast, P. (July 1980). "Préparation de nouveaux difluorodioxophosphates à partir de l'oxyde de difluorure de phosphoryle. Partie II. Réactions sur les acides iodique et periodique". Journal of Fluorine Chemistry 16 (1): 89–96. doi:10.1016/s0022-1139(00)85151-9. 
  38. ↑ 38.0 38.1 Eisenberg, Max; Desmarteau, Darryl D. (August 1972). "Xenon(II) difluorophosphates. Preparations, properties, and evidence for the difluorophosphate free radical". Inorganic Chemistry 11 (8): 1901–1904. doi:10.1021/ic50114a033. 
  39. ↑ Matsumoto, Kazuhiko; Okawa, Takeshi; Hagiwara, Rika (2012). "The Crystal to Plastic Crystal Phase Transition of Tetraethylammonium Difluorophosphate and Tetrafluoroborate". Chemistry Letters 41 (4): 394–396. doi:10.1246/cl.2012.394. 
  40. ↑ 40.0 40.1 40.2 40.3 Matsumoto, Kazuhiko; Hagiwara, Rika (3 August 2009). "A New Series of Ionic Liquids Based on the Difluorophosphate Anion". Inorganic Chemistry 48 (15): 7350–7358. doi:10.1021/ic9008009. PMID 19580312. 
  41. ↑ Eriks, K.; Wang, H. H.; Reed, P. E.; Beno, M. A.; Appelman, E. H.; Williams, J. M. (15 February 1985). "Di(3,3′,4,4′-tetramethyl-2,2′,5,5′-tetraselenafulvalenium)difluorophosphate, (C10H12Se4)2PO2F2, at 293 and 125 K". Acta Crystallographica Section C 41 (2): 257–260. doi:10.1107/S0108270185003535. https://zenodo.org/record/1236094. 
  42. ↑ Lange, Willy; Livingston, Ralph (March 1950). "Studies of Fluorophosphoric Acids and their Derivatives. XIV. Preparation of Anhydrous Difluorophosphoric Acid". Journal of the American Chemical Society 72 (3): 1280–1281. doi:10.1021/ja01159a057. 
  43. ↑ Semmoud, A.; Benghalem, A.; Addou, A. (January 1990). "Acide difluorophosphorique: nouvelle préparation". Journal of Fluorine Chemistry 46 (1): 1–6. doi:10.1016/S0022-1139(00)81555-9. 
  44. ↑ Vast, P.; Semmoud, A.; Addou, A.; Palavit, G. (March 1985). "Nouvelle méthode de preparation de l'acide difluorophosphorique". Journal of Fluorine Chemistry 27 (3): 319–325. doi:10.1016/S0022-1139(00)81312-3. 
  45. ↑ Zeng, Xiaoqing; Gerken, Michael; Beckers, Helmut; Willner, Helge (17 June 2010). "ChemInform Abstract: Spectroscopic and Structural Studies of Difluorophosphoryl Azide F2P(O)N3, Difluorophosphoryl Isocyanate F2P(O)NCO, and Difluorophosphoric Acid Anhydride, F2(O)POP(O)F2". ChemInform 41 (28): no. doi:10.1002/chin.201028001.  Originally in Inorg. Chem. 49 (2010) 6, 3002–3010
  46. ↑ Robinson, E. A. (September 1962). "The Preparation and Raman Spectrum of Diphosphoryl Tetrafluoride: Comparison with the Spectrum of Diphosphoryl Tetrachloride". Canadian Journal of Chemistry 40 (9): 1725–1729. doi:10.1139/v62-264. 
  47. ↑ Dehnicke, Kurt; Shihada, Abdel-Fattah (1976). "Structural and bonding aspects in phosphorus chemistry—inorganic derivatives of oxohalogeno phosphoric acids". Electrons in Oxygen- and Sulphur-Containing Ligands Structure and Bonding. Structure and Bonding 28: 51–82. doi:10.1007/3-540-07753-7_2. ISBN 978-3-540-07753-4. 
  48. ↑ Christe, K. O.; GNANN, R.; WAGNER, R. I.; WILSON, W. W. (4 August 2010). "ChemInform Abstract: The (PO2F2×2 AsF5)− Anion, an Example of a Stable, Oxygen- Bridged, 1:2 Donor-Acceptor Polynuclear Anion". ChemInform 28 (2): no. doi:10.1002/chin.199702025.  Full article at Eur. J. Solid State Inorg. Chem. 33 (1996) 9, 865–877
  49. ↑ Olah, Georg; Oswald, Alexius; Kuhn, Stephan (4 August 1959). "Untersuchung organischer Phosphorverbindungen. III. Darstellung von Difluorphosphorsäure- und von Difluorthiophosphorsäure-alkylamiden". Justus Liebigs Annalen der Chemie 625 (1): 88–91. doi:10.1002/jlac.19596250111. 



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