Phosphorofluoridate
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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 Tutton's salts are a family of salts with the formula M2M'(SO4)2(H2O)6 (sulfates) or M2M'(SeO4)2(H2O)6 (selenates). These materials are double salts, which means that they contain two different cations, M+ and M'2+ crystallized in the same regular ...
and
langbeinites Langbeinites are a family of crystalline substances based on the structure of langbeinite with general formula , where M is a large univalent cation (such as potassium, rubidium, caesium, or ammonium), and M' is a small divalent cation (for examp ...
. The most well-known compound of monofluorophosphate is
sodium monofluorophosphate Sodium monofluorophosphate, commonly abbreviated SMFP, is an inorganic compound with the chemical formula Na2PO3F. Typical for a salt, MFP is odourless, colourless, and water-soluble. This salt is an ingredient in some toothpastes.Klaus Schrödter ...
, commonly used in toothpaste. Related ions include
difluorophosphate Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula . It has a single negative charge and resembles perchlorate () and monofluorosulfonate (SO3F−) in shape and compounds. These ions are isoelectronic, a ...
() and
hexafluorophosphate Hexafluorophosphate is an anion with chemical formula of . It is an octahedral species that imparts no color to its salts. is isoelectronic with sulfur hexafluoride, , and the hexafluorosilicate dianion, , and hexafluoroantimonate . In this anio ...
(). The related neutral molecule is phosphenic fluoride PO2F. Organic derivatives can be highly toxic and include
diisopropyl fluorophosphate Diisopropyl fluorophosphate (DFP) or Isoflurophate is an oily, colorless liquid with the chemical formula C6H14FO3P. It is used in medicine and as an organophosphorus insecticide. It is stable, but undergoes hydrolysis when subjected to moisture. ...
. Some of the
Novichok agent Novichok (russian: Новичо́к, lit=newcomer, novice, newbie) is a group of nerve agents, some of which are binary chemical weapons. The agents were developed at the GosNIIOKhT state chemical research institute by the Soviet Union and Ru ...
s 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 protease Serine proteases (or serine endopeptidases) are enzymes that cleave peptide bonds in proteins. Serine serves as the nucleophilic amino acid at the (enzyme's) active site. They are found ubiquitously in both eukaryotes and prokaryotes. ...
s irreversibly. This prevents these enzymes from functioning. Such an important enzyme is
acetylcholinesterase Acetylcholinesterase (HGNC symbol ACHE; EC 3.1.1.7; systematic name acetylcholine acetylhydrolase), also known as AChE, AChase or acetylhydrolase, is the primary cholinesterase in the body. It is an enzyme Enzymes () are proteins that a ...
as found in most animals. Some of the organic esters are detoxified in mammals by an enzyme in the blood and liver called
paraoxonase Paraoxonases are a family of mammalian enzymes with aryldialkylphosphatase activity. There are three paraoxonase isozymes, which were originally discovered for their involvement in the hydrolysis of organophosphates. Research has indicated the ...
PON1 Serum paraoxonase and arylesterase 1 (PON1) also known as A esterase , homocysteine thiolactonase or serum aryldialkylphosphatase 1 is an enzyme that in humans is encoded by the ''PON1'' gene. Paraoxonase 1 has esterase and more specifically parao ...
. 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 Sarin (NATO designation GB G-series, "B"">Nerve_agent#G-series.html" ;"title="hort for Nerve agent#G-series">G-series, "B" is an extremely toxic synthetic organophosphorus compound.SnO Tin(II) oxide (stannous oxide) is a compound with the formula SnO. It is composed of tin and oxygen where tin has the oxidation state of +2. There are two forms, a stable blue-black form and a metastable red form. Preparation and reactions Blue ...
, 40% SnF2, 50% P2O5 forms a glass melting about 139 °C.
PbO Lead(II) oxide, also called lead monoxide, is the inorganic compound with the molecular formula Pb O. PbO occurs in two polymorphs: litharge having a tetragonal crystal structure, and massicot having an orthorhombic crystal structure. Modern ap ...
and PbF2 can lower the melting temperature, and increase water resistance. These glasses can also be coloured by various other elements, and organic dyes. Some
mixed anion compounds Mixed anion compounds, heteroanionic materials or mixed anion materials are chemical compounds containing cations and more than one kind of anion. The compounds contain a single phase, rather than just a mixture. Use in materials science By havin ...
are known with other anions like
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts typ ...
, chloride, difluorophosphate or
tetrafluoroborate Tetrafluoroborate is the anion . This tetrahedral species is isoelectronic with tetrafluoroberyllate (), tetrafluoromethane (CF4), and tetrafluoroammonium () and is valence isoelectronic with many stable and important species including the perchl ...
.


Production

Hydrolysis of
difluorophosphate Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula . It has a single negative charge and resembles perchlorate () and monofluorosulfonate (SO3F−) in shape and compounds. These ions are isoelectronic, a ...
with an alkali produces monofluorophosphate. : + 2 MOH → M2PO3F + H2O + F Industrial production is by reaction of a
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts typ ...
with a
metaphosphate A metaphosphate ion is an oxyanion that has the empirical formula . It was first postulated in 1955 but was not observed until 1979, when it was detected by mass spectrometry. Metaphosphate is an intermediate in the hydrolysis of phosphate esters b ...
. :MF + MPO3 → M2PO3F
Disodium hydrogen phosphate Disodium phosphate (DSP), or disodium hydrogen phosphate, or sodium phosphate dibasic, is the inorganic compound with the formula Na2HPO4. It is one of several sodium phosphates. The salt is known in anhydrous form as well as forms with 2, 7, 8, ...
or
tetrasodium pyrophosphate Tetrasodium pyrophosphate, also called sodium pyrophosphate, tetrasodium phosphate or TSPP, is an inorganic compound with the chemical formula, formula Na4P2O7. As a salt, it is a white, water-soluble solid. It is composed of pyrophosphate anion an ...
can react with hydrogen fluoride to form the sodium salt. :Na2HPO4 or Na4P2O7 Phosphoric acid reacts with metal fluorides dissolved in molten
urea Urea, also known as carbamide, is an organic compound with chemical formula . This amide has two amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest amide of carbamic acid. Urea serves an important r ...
to yield monofluorphosphates.


Properties

Monofluorophosphates are stable at room temperature, but will decompose when heated. For example, at ,
silver monofluorophosphate Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical co ...
gives off
phosphoryl fluoride Phosphoryl fluoride (commonly called phosphorus oxyfluoride) is a compound with the chemical formula . It is a colorless gas that hydrolyzes rapidly. Synthesis and reactions Phosphorus oxyfluoride is prepared by partial hydrolysis of phosphorus p ...
(POF3) as a gas leaving behind
silver phosphate Silver phosphate or silver orthophosphate is a light sensitive, yellow, water-insoluble chemical compound composed of silver and phosphate ions of formula Ag3PO4. Synthesis, reactions and properties Silver phosphate is formed as a yellow solid p ...
(Ag3PO4) and
silver pyrophosphate Silver phosphate or silver orthophosphate is a light sensitive, yellow, water-insoluble chemical compound composed of silver and phosphate ions of formula Ag3PO4. Synthesis, reactions and properties Silver phosphate is formed as a yellow solid p ...
(Ag4P2O7). 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. Most commonly the monofluorophosphtae ion takes on point group 1, but a significant number have point group ''m''. Only two are known with 3''m'' and one with 3. 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.


Compounds


Organic


Uses

Zinc monofluorophosphate can be used as a corrosion inhibitor for steel when salt is present. Glutamine monofluorophosphate has been used as a fluoride-bearing medicine.


References


Other reading

*{{cite journal, last1=Leblanc, first1=Marc, first2=Vincent, last2=Maisonneuve, first3=Alain, last3=Tressaud, year=2014, title=Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and Oxide-Fluorides, journal=Chemical Reviews, issn=0009-2665, doi=10.1021/cr500173c, volume=115, issue=2, pages=1191–1254, pmid=25135645 Phosphorus oxyanions Fluorophosphates Anions