Monofluorophosphate

Monofluorophosphate is an anion with the formula PO3F2−, which is a phosphate group with one oxygen atom substituted with a fluoride atom. The charge of the ion is −2. The ion resembles sulfate in size, shape and charge, and can thus form compounds with the same structure as sulfates. These include Tutton's salts and langbeinites. The most well-known compound of monofluorophosphate is sodium monofluorophosphate, commonly used in toothpaste.

Monofluorophosphate
Structure of fluorophosphonate ion

Names
IUPAC name
Fluoro-dioxido-oxo-λ5-phosphane
Other names
  • Fluorophosphate
  • Fluorophosphonate
  • Monofluorophosphate
  • Phosphorofluoridate
Identifiers
3D model (JSmol)
ChemSpider
UNII
  • InChI=1S/FH2O3P/c1-5(2,3)4/h(H2,2,3,4)/p-2
    Key: DWYMPOCYEZONEA-UHFFFAOYSA-L
  • [O-]P(=O)([O-])F
Properties
PO3F2−
Molar mass 97.971 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Related ions include difluorophosphate (PO2F−2) and hexafluorophosphate ([PF6]−).[1] The related neutral molecule is phosphenic fluoride PO2F.

Organic derivatives can be highly toxic and include diisopropyl fluorophosphate. Some of the Novichok agents are monofluorophosphate esters. Names are given to these by naming the groups attached as esters and then adding "fluorophosphonate" to the end of the name. Two organic groups can be attached. Other related nerve gas substances may not be esters, and instead have carbon-phosphorus or nitrogen-phosphorus bonds. The organic fluorophosphonates react with serine esterases and serine proteases irreversibly. This prevents these enzymes from functioning. Such an important enzyme is acetylcholinesterase as found in most animals.[2] Some of the organic esters are detoxified in mammals by an enzyme in the blood and liver called paraoxonase PON1.[3]

Willy Lange from Berlin discovered sodium monofluorophosphate in 1929. He fruitlessly tried to make monofluorophosphoric acid. However, he did discover the highly toxic organic esters. Following this discovery various nerve gases like sarin were developed.

Fluorophosphate glasses are low melting point kinds of glass which are mixtures of fluoride and phosphate metal compounds. For example, the composition 10% SnO, 40% SnF2, 50% P2O5 forms a glass melting about 139 °C. PbO and PbF2 can lower the melting temperature, and increase water resistance.[4] These glasses can also be coloured by various other elements, and organic dyes.

Some mixed anion compounds are known with other anions like fluoride, chloride, difluorophosphate or tetrafluoroborate.

Production

Hydrolysis of difluorophosphate with an alkali produces monofluorophosphate.

PO2F−2 + 2 MOH → M2PO3F + H2O + F−

Industrial production is by reaction of a fluoride with a metaphosphate.

MF + MPO3 → M2PO3F

Disodium hydrogen phosphate or tetrasodium pyrophosphate can react with hydrogen fluoride to form the sodium salt.

Na2HPO4 or Na4P2O7

Phosphoric acid reacts with metal fluorides dissolved in molten urea to yield monofluorophosphates.[5]

Properties

Monofluorophosphates are stable at room temperature, but will decompose when heated. For example, at 450 K (177 °C), silver monofluorophosphate gives off phosphoryl fluoride (POF3) as a gas leaving behind silver phosphate (Ag3PO4) and silver pyrophosphate (Ag4P2O7).[6]

In inorganic compounds the monofluorophosphate ion has an average P–O bond length of 1.51 Å. The P–F bond is longer, on average 1.58 Å. The O P F angle is 104.8°, smaller than the tetrahedral 109.47°. To compensate the O P O bond angle is 113.7° on average.[7]

Most commonly the monofluorophosphtae ion takes on point group 1, but a significant number have point group m. Only two are known with 3m and one with 3.[7]

When compared to sulfates, some are isotypical with the monofluorophosphates. Yet others have sulfates that take on a different form. But most know monofluorophosphates have no known equivalent sulfate.[7]

Compounds
Name Formula Crystal form Formula weight Density Comment ChemSpider PubChem CAS
fluorophosphoric acid H2PO3F 99.986 22687 24267 13537-32-1
[8] BePO3F-I Pc a=4.9331 b=6.6283 c=4.7083 β=90.2007 Z=2 band gap 8.03 eV SHG 1.72×KDP
[8] BePO3F-II P63 a=4.9651 c=9.3236 Z=2
[8] BePO3F-III Cc a=4.9542 b=8.5812 c=10.0532 β=98.0674 Z=4
[8] BePO3F-IV Cc a=8.5892 b=4.9532 c=10.1526 β=92.4967 Z=4
[8] BePO3F-V Cm a=9.2837 b=5.1602 c=7.1809 β=143.9321 Z=2
[8] BePO3F-VI P63mc a=5.1519 c=8.8598 Z=2
ammonium monofluorophosphate[9] (NH4)2PO3F orthorhombic: a = 6.29 Å, b = 8.31 Å, c = 12.70 Å, β = 99.6°, Z = 4[10] 134.05 1.633 8324505
ammonium monofluorophosphate hydrate[11] (NH4)2PO3F·H2O monoclinic: a = 7.9481 Å, b = 11.3472 Å, c = 6.0425 Å, β = 117.55°, Z = 4
monoclinic: a = 6.3042 Å, b = 8.2942 Å, c = 12.760 Å, β = 98.415°, Z = 4, V = 657.416 Å3[12]		 152.05 1.536
ammonium tetrafluoroborate-monofluorophosphate[13] (NH4)3[PO3F][BF4] monoclinic P21/m: a = 7.8384 Å, b = 6.0996 Å, c = 9.9079 Å, β = 111.990°, V = 439.24 Å3, Z = 2 238.91 1.806
[14] (N2H6)[HPO3F]2 monoclinic C12/c1 a=14.1326 b=7.0340 c=7.9877 β=96.763 Z=4 788.52 1.954 colourless; large birefringence
sodium monofluorophosphate Na2PO3F 22686 24266 10163-15-2
sodium hydrogen monofluorophosphate NaHPO3F 121.968 19860808 20859-36-3
sodium hydrogen monofluorophosphate dihydrate[15] NaHPO3F·2H2O monoclinic: a = 19.112 Å, b = 5.341 Å, c = 12.72 Å, α = 110.18°, V = 1219.4 Å3 167.01 1.819
magnesium monofluorophosphate MgPO3F 122.28 23206079
diammonium manganese dimonofluorophosphate dihydrate[7] (NH4)2Mg(PO3F)2·2H2O monoclinic C2/m: a = 13.374 Å, b = 5.3541 Å, c = 7.385 Å, β = 113.758°, V = 484.01 Å3, Z = 2 292.37 2.006
potassium monofluorophosphate[9] K2PO3F orthorhombic: a = 7.554 Å, b = 5.954 Å, c = 10.171 Å, V = 457 Å3, Z = 4 (at 20 °C)[16] 176.17 2.57 20859-37-4 14306-73-1
K2PO3F·KF[17]
Potassium hydrogen monofluorophosphate KHPO3F monoclinic: a = 7.273 Å, b = 14.086 Å, c = 7.655 Å, β = 90.13°, Z = 8, V = 784.233 Å3[18]
Tripotassium hydrogen monofluorophosphate K3H(PO3F)2 monoclinic: a = 7.973 Å; b = 11.635 Å; c = 9.668 Å, β = 113.52°, Z = 4, V = 822.35 Å3[18]
Ammonium dipotassium hydrogen difluorophosphate[19] NH4K2H(PO3F)2
calcium monofluorophosphate dihydrate[20] CaPO3F·2H2O triclinic: a = 8.6497 Å, b = 6.4614 Å, c = 5.7353 Å, α = 119.003°, β = 110.853°, γ = 94.146°, V = 249.943 Å3, Z = 2[12] 2.313 8096036 9920401 37809-19-1
calcium monofluorophosphate hemihydrate[20] CaPO3F·0.5H2O
vanadium monofluorophosphate VPO3F 148.91 20452625
chromium(III) monofluorophosphate[7] Cr2(PO3F)3·18.8H2O triclinic: a = 11.594 Å, b = 15.292 Å, c = 15.360 Å, α = 83.804°, β = 84.203, γ = 82.597, V = 2674.1 Å3, Z = 4 736.88 1.830
ammonium chromium(III) difluorophosphate hexahydrate[7] NH4Cr(PO3F)2·6H2O R3m: a = 6.5491 Å, c = 25.438 Å, Z = 3 9.4489 1.972 green
manganese(II) fluorophosphate dihydrate MnPO3F·2H2O triclinic: a = 5.528 Å, b = 5.636 Å, c = 8.257 Å, α = 81.279°, β = 75.156°, γ = 71.722°, Z = 2[21] 188.94
diammonium manganese monofluorophosphate[7] (NH4)2Mn(PO3F)2·2H2O monoclinic: P21/n a = 12.558 Å, b = 5.5456 Å, c = 7.422 Å, β = 99.918°, Z = 2 500.9 2.142 pink
ammonium trimanganese dimonofluorophosphate difluorophosphate difluoride[22] (NH4)Mn3(PO3F)2(PO2F2)F2 monoclinic: a = 20.3151 Å, b = 7.6382 Å, c = 7.8312 Å, β = 103.589°, V = 1181.16 Å3 517.8 2.9116
diammonium cobalt dimonofluorophosphate dihydrate[7] (NH4)2Co(PO3F)2·2H2O monoclinic C2/m: a = 13.386 Å, b = 5.3476 Å, c = 7.390 Å, β = 114.02°, V = 483.2 Å3, Z = 2 326.99 2.247
ammonium tricobalt dimonofluorophosphate difluorophosphate difluoride[22] (NH4)Co3(PO3F)2(PO2F2)F2 monclinic: a = 19.9678 Å, b = 7.4883 Å, c = 7.5679 Å, β = 102.676°, V = 1104.01 Å3 529.7 3.1871
Diammonium nickel dimonofluorophosphate hexahydrate[7] (NH4)2Ni(PO3F)2·6H2O monoclinic: a = 6.2700 Å, b = 12.2845 Å, c = 9.1894 Å, β = 106.033°, Z = 2 680.27 1.947 blue Tutton
copper monofluorophosphate[23] CuPO3F·5H2O 251.59
basic copper potassium monofluorophosphate[23] Cu2K(OH)(PO3F)2·5H2O monoclinic: a = 9.094 Å, b = 6.333 Å, c = 7.75 Å, β = 117.55°, Z = 2 natrochalcite
diammonium diaquabis(monofluorophosphato) copper[24] Cu(NH4)2(PO3F)2·2H2O monoclinic: a = 13.454 Å, b = 5.243 Å, c = 7.518 Å, β = 114.59°, V = 482.2 Å3, Z = 2 331.6 2.28
basic tetraammonium dicopper dimonofluorophosphate[7] NH4Cu2OH(PO3F)2·H2O C2/m: a = 9.1012 Å, b = 6.4121 Å, c = 7.8506 Å, β = 116.277°, Z = 2 410.80 3.040 light blue natrochalcite
zinc monofluorophosphate[25][7] ZnPO3F·2.5H2O triclinic: a = 7.6020 Å, b = 7.6490 Å, c = 9.4671 Å, α = 88.633°, β = 88.888°, γ = 87.182°, V = 549.58 Å3, Z = 4 163.35 2.518 20846323 68705-59-9
anhydrous diammonium zinc tetramonofluorophosphate[7] (NH4)2Zn3(PO3F)4 cubic: a = 11.4769 Å
diammonium zinc dimonofluorophosphate[7] (NH4)2Zn(PO3F)2·0.2H2O monoclinic C2/c: a = 18.936 Å, b = 7.6955 Å, c = 20.528 Å, β = 108.641° Z = 12 2834.4 2.117 colourless
diammonium trizinc tetramonofluorophosphate[7] (NH4)2Zn3(PO3F)4·H2O cubic I43d: a = 11.3693 Å, Z = 4 1469.6 2.902 colourless
rubidium monofluorophosphate[26] Rb2PO3F orthorhombic:[27] a = 7.8714 Å, b = 6.1236 Å, c = 10.5424 Å, V = 508.15 Å3, Z = 4 (at 17 °C) 268.9 3.514
Rubidium hydrogen monofluorophosphate RbHPO3F monoclinic: a = 7.465 Å, b = 15.551 Å, c = 7.563 Å, β = 105.38°, V = 846.533 Å3, Z = 8[18]
[28] Na1.5Rb0.5PO3F·H2O orthorhombic Pmn21: a = 6.015 Å, b = 8.965 Å, c = 4.9689 Å, Z = 2 267.97 2.398 colourless
strontium monofluorophosphate SrPO3F monoclinic[29] 185.59 18183579
strontium monofluorphosphate hydrate[30] SrPO3F·H2O 185.59
silver monofluorophosphate[23] Ag2PO3F monoclinic: a = 9.245 Å, b = 5.585 Å, c = 14.784 Å, β = 90.178°, Z = 8[6] 313.7 44135907
trisilver ammonium monofluorophosphate NH4Ag3(PO3F)2 monoclinic: a = 30.895 Å, b = 5.5976 Å, c = 9.7522 Å, β = 90.027°, V = 1686.6 Å3, Z = 8[31] 537.59 4.234
cadmium monofluorophosphate[7] CdPO3F·2H2O triclinic P1_: a = 5.2678 Å, b = 6.6697 Å, c = 7.7037 Å, α = 65.506°, β = 85.919°, γ = 75.394°, V = 238.584 Å3, Z = 2 246.40 3.430
cadmium ammonium monofluorophosphate chloride dihydrate[32] Cd2.5(NH4)2(PO3F)3Cl·2H2O colourless
tin monofluorophosphate SnPO3F·2.5H2O monoclinic 216.68 44717639 52262-58-5
caesium monofluorophosphate Cs2PO3F[26] orthorhombic: a = 8.308 Å, b = 6.3812 Å, c = 11.036 Å, V = 585.1 Å3, Z = 4 (at −33 °C) 363.8 4.129
caesium hydrogen monofluorophosphate CsHPO3F monoclinic: a = 14.478 Å, b = 5.929 Å, c = 5.413 Å, β = 103.30°, V = 452.2 Å3, Z = 4[33] 231.89
tricaesium diammonium hydrogen monofluorophosphate Cs3(NH4)2H3(PO3F)4 monoclinic: a = 20.619 Å, b = 12.076 Å, c = 15.856 Å, β = 102.58°, V = 3853 Å3, Z = 8[33] 829.72
barium monofluorophosphate BaPO3F monoclinic: a = 11.3105 Å, b = 8.6934 Å, c = 9.2231 Å, β = 127.819°, Z = 4
orthorhombic[34]		 235.299 20836124 15600-53-0[35]
Mercurous monofluorophosphate Hg2PO3F orthorhombic: a = 9.406 Å, b = 12.145 Å, c = 8.567 Å, V = 978.7 Å3, Z = 8[36]
lead monofluorophosphate PbPO3F orthorhombic: a = 6.95 Å, b = 8.52 Å, c = 5.47 Å[37] 6.24
dilead monofluorophosphate dichloride hydrate[7] Pb2(PO3F)Cl2·H2O orthorhombic Pnma: a = 20.486 Å, b = 5.3967 Å, c = 6.9722 Å, V = 770.8 Å3, Z = 4 601.27 5.181
ditheylammonium hydrogen monofluorophosphate[15] [NH2(CH2CH3)2]HPO3F orthorhombic: a = 12.892 Å, b = 9.530 Å, c = 13.555 Å, α = 90°, V = 1665 Å3 173.12 1.381
tetramethylammonium monofluorophosphate[15] [N(CH3)4]2PO3F 246.26
tetraethylammonium monofluorophosphate[15] [N(CH2CH3)4]2PO3F 358.47
tetrabutylammonium monofluorophosphate[15] [N(CH2CH2CH2CH3)4]2PO3F 582.90
piperazinium hydrogen monofluorophosphate[15] [PipzH2]HPO3F monoclinic: a = 6.020 Å, b = 13.012 Å, c = 7.285 Å, α = 95.09°, V = 568.4 Å3 286.11 1.672
glutamine monofluorophosphate monohydrate C5H12N2O3PFO3 246.131 19989732
glutamine monofluorophosphate disodium dichloride C10H20Cl2FN4Na2O9P 507.146 143826 164002
anilinium hydrogen monofluorophosphate[38] [C6H8N]+[HPO3F]− monoclinic: a = 9.418 Å, b = 14.31 Å, c = 6.303 Å, β = 92.45°, V = 859 Å3, Z = 4 193.12 1.51
Tris(2-carbamoylguanidinium) hydrogen fluorophosphonate fluorophosphonate monohydrate[39] [C2H7N4O+]3[HPO3F]−[PO3F]2−·H2O triclinic: a = 6.7523 Å, b = 8.2926 Å, c = 9.7297 Å, α = 100.630°, β = 90.885°, γ = 99.168°, V = 528.05 Å3
bis(2-carbamoylguanidinium) fluorophosphonate dihydrate[40] [C2H7N4O+]2[PO3F]2−·2H2O

Organic
Name Formula Formula weight ChemSpider PubChem CAS
dimethyl fluorophosphate (CH3)2PO2F 128.039 72304 80052 5954-50-7
methyl ethyl fluorophosphate (CH3)(CH3CH2)PO2F
1-[ethoxy(fluoro)phosphoryl]oxyethane[41] (CH3CH2)2PO2F 156.093 67752 358-74-7
isoflurophate [(CH3)2CH]2PO2F 184.147 5723 5936 55-91-4
1-[fluoro(2-oxopropoxy)phosphoryl]oxypropan-2-one 212.113 129718773
isobutyl methyl fluorophosphate[42] 170.12 129684440
1-[fluoro(methoxy)phosphoryl]oxypentane (CH3)(CH3CH2CH2CH2CH2)PO3F 184.147 129761096
1-[fluoro(propoxy)phosphoryl]oxypropane (CH3CH2CH2)2PO3F 184.147 4954063 6451603 381-45-3
O-isopropyl propyl fluorophosphonate (CH3)2CH(CH3CH2CH2)PO3F 184.147 88538036
O-1-methylbutyl ethyl fluorophosphonate 198.174 129761095
dibutyl fluorophosphate (CH3CH2CH2CH2)2PO3F 212.201 11640560 13025172 674-48-6
di-sec-butyl fluorophosphate [CH3CH2CH(CH3)]2PO3F 212.201 92528 102452 625-17-2
di(1,3-dimethyl-n-butyl) fluorophosphate [(CH3)2CHCH2CH(CH3)]2PO3F 268.309 91838 101643 311-60-4
1-[fluoro(2-methylpentan-3-yloxy)phosphoryl]oxyoctane 296.363 129760905
methyl arachidonoyl fluorophosphonate 400.471 11741711 9916415
12-[fluoro(propan-2-yloxy)phosphoryl]oxydodec-1-ene 308.374 129892247
bis(4-phenylbutyl) fluorophosphate (C6H5CH2CH2CH2CH2)2PO3F 364.397 162961 187452 85473-46-7
3′-fluoro-3′-deoxythymidine 5′-fluorophosphate 326.193 2339398 3081896 152829-59-9
cytidine 5′-fluorophosphate 325.189 87861929 68521-86-8
chlorofluoromethylideneamino-2-chloroethyl fluorophosphate ClFC=NClCH2CH2PO3F A-230 Novichok agent[43]
chlorofluoromethylideneamino-1-methyl-2-chloroethyl fluorophosphate ClFC=NClCH2CH(CH3)PO3F A-232 Novichok agent
chlorofluoromethylideneamino-1,2-dimethyl-2-chloroethyl fluorophosphate ClFC=NCl(CH3)CHCH(CH3)PO3F A-234 Novichok agent

Uses

Zinc monofluorophosphate can be used as a corrosion inhibitor for steel when salt is present.[44]

Glutamine monofluorophosphate has been used as a fluoride-bearing medicine.

References
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Other reading
  • Leblanc, Marc; Maisonneuve, Vincent; Tressaud, Alain (2014). "Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and Oxide-Fluorides". Chemical Reviews. 115 (2): 1191–1254. doi:10.1021/cr500173c. ISSN 0009-2665. PMID 25135645.
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