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]

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]

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

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]

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]

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">Phosphoryl chloride difluoride</span> Chemical compound

Phosphoric chloride difluoride POF2Cl is a colourless gas. At one atmosphere pressure the gas condenses to a liquid at 3.1 °C and freezes at −96.4. Alternate names are difluorophosphoryl chloride or phosphoryl chloride difluoride.

<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.

<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

  1. ↑ Toy, Arthur D. F. (22 Oct 2013). The Chemistry of Phosphorus. Pergamon Texts in Inorganic Chemistry. Vol. 3. Pergamon Press. pp. 536–537. ISBN   9781483147413 . Retrieved 19 June 2015.
  2. 1 2 3 4 5 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. Bibcode:1959Natur.183.1517A. doi:10.1038/1831517a0. PMID   13666792. S2CID   4291858.
  3. 1 2 3 4 5 6 7 Lange, Willy (3 April 1929). "Über die Difluorphosphorsäure und ihre der Perchlorsäure ähnliche Salzbildung" [On difluorophosphoric acid and its perchlorate-like salt formation]. Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 62 (4): 786–792. doi:10.1002/cber.19290620408.
  4. 1 2 3 4 5 6 7 8 9 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. 1 2 3 4 5 6 7 8 9 10 11 12 13 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" [Methodical study of the synthesis of metal difluorodioxophosphates from phosphoryl difluoride oxide]. Journal of Fluorine Chemistry. 38 (3): 297–302. doi:10.1016/S0022-1139(00)81065-9.
  6. 1 2 3 4 5 6 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. 1 2 3 4 Weidlein, J. (April 1968). "Darstellung, Eigenschaften und IR-Spektren von OTi(O2PCl2)2, Fe(O2PF2)3 und In(O2PF2)3" [Description, properties and IR spectra of...]. Zeitschrift für anorganische und allgemeine Chemie. 358 (1–2): 13–20. doi:10.1002/zaac.19683580103.
  8. 1 2 Shihada, Abdel-Fattah; Mohammed, Abdulalah T. (1 January 1980). "Zur Reaktion von Trimethylsilyl-difluorophosphat, Trimethylsilyl-dimethylphosphinat und Difluorophosphorsäureanhydrid mit TiCl4 bzw. SbCl5" [On the Reactions of Trimethylsilyl Difluorophosphate, Trimethylsilyl Dimethylphosphinate and Difluorophosphoric Acid Anhydride with TiCl4 and SbCl5]. Zeitschrift für Naturforschung B. 35 (1): 60–63. doi: 10.1515/znb-1980-0114 . S2CID   96302051.
  9. 1 2 3 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" [Preparation of new difluorodioxophosphates from phosphoryl difluorideoxide. Part V. Reactions with uranium dioxide]. 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" [Local symmetry force-field of oxyfluorine compounds of phosphorus(V). I. Alkali difluorodioxophosphates (DFP)]. Spectrochimica Acta Part A: Molecular Spectroscopy. 38 (7): 785–790. Bibcode:1982AcSpA..38..785A. doi:10.1016/0584-8539(82)80068-8.
  11. 1 2 3 4 5 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. 1 2 Vast, P.; Semmoud, A. (June 1994). "Comportement thermique du difluorodioxophosphate ferreux" [Thermal behaviour of ferrous difluorodioxophosphate]. Journal of Thermal Analysis. 41 (6): 1489–1493. doi:10.1007/bf02549945. S2CID   95079191.
  13. ↑ Vast, P.; Semmoud, A.; Palavit, G. (December 1986). "Préparation de l'acide monofluorotrioxophosphorique H2PO3F à partir de l'acide difluorodioxophosphorique HPO2F2" [Preparation of monofluorotrioxophosphoricacid H2PO3F from difluorodioxophosphoric acid HPO2F2]. Journal of Fluorine Chemistry. 34 (2): 229–232. doi:10.1016/s0022-1139(00)85072-1.
  14. 1 2 3 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. 1 2 3 4 5 6 7 8 9 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. 1 2 3 Roesky, Herbert W. (July 1967). "Über Reaktionen mit Pyrophosphoryltetrafluorid" [On Reactions with pyrophosphoryl tetrafluoride]. Chemische Berichte. 100 (7): 2147–2150. doi:10.1002/cber.19671000706.
  19. 1 2 3 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" [Preparation of new difluorodioxophosphates from phosphoryl difluoride oxide. Part I. Reactions with nitrogen oxides]. Journal of Fluorine Chemistry. 14 (2): 163–169. doi:10.1016/S0022-1139(00)82884-5.
  20. 1 2 3 4 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)". Dalton Transactions. 50 (29): 10206–10213. doi:10.1039/D1DT00698C. ISSN   1477-9226. PMID   34231608. S2CID   235758275.
  21. 1 2 3 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 [S2O7]2− and [PO2F2]− groups". Dalton Transactions. 49 (48): 17658–17664. doi:10.1039/D0DT03307C. ISSN   1477-9226. PMID   33231582. S2CID   227157666.
  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" [Salts of halophosphoric acids. V. Description and structure of bis(ethylacetate)calcium difluorophosphate...]. Zeitschrift für anorganische und allgemeine Chemie. 365 (5–6): 294–300. doi:10.1002/zaac.19693650509.
  25. 1 2 3 4 5 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. 1 2 3 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. 1 2 3 4 5 6 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. PMC   7336792 . PMID   32695441.
  29. 1 2 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. 1 2 3 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" [Investigations upon dialkylmetal phosphate and phosphite derivatives of the elements aluminium, gallium, indium and thallium. II. The vibrational spectroscopy of difluoro- and dichlorophosphates]. Zeitschrift für anorganische und allgemeine Chemie. 403 (3): 301–309. doi:10.1002/zaac.19744030309.
  32. 1 2 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" [Synthesis of copper und silver complexes with pentadentate N,S- und hexadentate N,O-chelation ligands – characterization und crystal structures of...]. Zeitschrift für anorganische und allgemeine Chemie. 623 (9): 1367–1374. doi:10.1002/zaac.19976230908.
  34. 1 2 3 Krüger, N.; Dehnicke, K.; Shihada, A.-F. (February 1978). "Difluorophosphate von Zinn(IV) und Antimon(V)" [Difluorophosphates of tin(IV) and antimony(V)]. Zeitschrift für anorganische und allgemeine Chemie. 438 (1): 169–175. doi:10.1002/zaac.19784380118.
  35. 1 2 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. 1 2 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" [Preparation of new difluorodioxophosphates from phosphoryl difluoride oxide. Part II. Reactions with iodic and periodic acids]. Journal of Fluorine Chemistry. 16 (1): 89–96. doi:10.1016/s0022-1139(00)85151-9.
  38. 1 2 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. hdl: 2433/259816 . S2CID   97011854.
  40. 1 2 3 4 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 .
  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" [Difluorophosphoric acid: new preparation]. 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" [New preparation method of difluorophosphoric acid]. 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" [Investigations of organic phosphorus compounds. III. description of difluorophosphoric and difluorothiophosphoric alkylamides]. Justus Liebigs Annalen der Chemie. 625 (1): 88–91. doi:10.1002/jlac.19596250111.
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