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{{Short description|Ion}}
{{for|phosphites of the type P(OR)<sub>3</sub>|Phosphite ester}}
{{Chembox {{Chembox
| ImageFile = Phosphite ion.svg
| verifiedrevid = 411474802
| ImageFileL1 = Phosphite-ion-from-xtal-3D-balls.png
| ImageFile =
| ImageFileR1 = Phosphite-ion-from-xtal-3D-vdW.png
| IUPACName = phosphite
| IUPACName = Phosphonate
| Section1 = {{Chembox Identifiers
| Verifiedfields = changed
| SMILES = P()()}}
| Watchedfields = changed
|Section2= {{Chembox Properties
| verifiedrevid = 415680520
| Formula=PO<sub>3</sub><sup>3-</sup>
| SystematicName = Phosphite<ref>{{Cite web|title = Phosphorite - PubChem Public Chemical Database|url = https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=107908|work = The PubChem Project|location = USA|publisher = National Center for Biotechnology Information}}</ref>
}}
| Section1 = {{Chembox Identifiers
| CASNo_Ref = {{cascite|changed|??}}
| CASNo = 15477-76-6
| PubChem = 406
| ChemSpiderID = 10449627
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| MeSHName = Phosphorite
| ChEBI_Ref = {{ebicite|changed|EBI}}
| ChEBI = 16215
| ChEMBL =
| ChEMBL_Ref = {{ebicite|changed|EBI}}
| Gmelin = 1618
| KEGG =
| SMILES = P()()=O
| SMILES_Comment = hypervalent form
| SMILES1 = ()()
| SMILES1_Comment = ionic form
| StdInChI = 1S/O3P/c1-4(2)3/q-3
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = AQSJGOWTSHOLKH-UHFFFAOYSA-N
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
}} }}
| Section2 = {{Chembox Properties
A '''phosphite''' a salt of ]. The '''phosphite''' ion (PO<sub>3</sub><sup>3−</sup>) is a ] with a ] central atom where ] has an ] of +3.<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref> Its molecular geometry is approximately ] like ].<ref name = "Loub">Crystal chemistry of inorganic phosphites, J. Loub, Acta Cryst. (1991), B47, 468-473, doi:10.1107/S0108768191002380 </ref>
| Formula = {{chem|HPO|3|2−}}
| MolarMass = 79.9810 g mol<sup>−1</sup>
}}
| Section3 = {{Chembox Related
| OtherAnions = ]<br />
]
}}
}}
A '''phosphite anion''' or '''phosphite''' in inorganic chemistry usually refers to <sup>2−</sup> but includes <sup>−</sup> (<sup>−</sup>). These anions are the conjugate bases of ] (H<sub>3</sub>PO<sub>3</sub>). The corresponding salts, e.g. ] (Na<sub>2</sub>HPO<sub>3</sub>) are reducing in character.


==Nomenclature==
Because ] exists as an equilibrium ] mixture of P(OH)<sub>3</sub> and HP(O)(OH)<sub>2</sub>, predominantly the latter, there is some confusion in nomenclature. The IUPAC recommends<ref name = "IUPAC inorganic">{{RedBook2005}}.</ref> that the trihydroxy form be called phosphorous acid and its salts phosphites, with the dihydroxy form being called phosphonic acid and its salts phosphonates, but despite this, salts of HP(O)(OH)<sub>2</sub> are often called phosphites rather than phosphonates.
The IUPAC recommended name for phosphorous acid is ]. Correspondingly, the IUPAC-recommended name for the {{chem|HPO|3|2−}} ion is ]. In the US the IUPAC naming conventions for inorganic compounds are taught at high school, but not as a 'required' part of the curriculum.<ref>Physical setting/ chemistry core curriculum, The University of the State of New York, The State Education Department, http://www.p12.nysed.gov/ciai/mst/pub/chemist.pdf {{Webarchive|url=https://web.archive.org/web/20180329090703/http://www.p12.nysed.gov/ciai/mst/pub/chemist.pdf |date=2018-03-29 }}</ref> A well-known university-level textbook follows the IUPAC recommendations.<ref name = "Wiberg&Holleman">Egon Wiberg, Arnold Frederick Holleman (2001) ''Inorganic Chemistry'', Elsevier {{ISBN|0-12-352651-5}}</ref> In practice any reference to "phosphite" should be investigated to determine the naming convention being employed.


==Salts containing HPO<sub>3</sub><sup>2−</sup>, called phosphonates or phosphites==
The term phosphite is also used to mean ], an ] compound with the formula P(OR)<sub>3</sub>.
:]. The anion has C<sub>3v</sub> symmetry.]]
From the commercial perspective, the most important phosphite salt is ]. Many salts containing the phosphite ion have been investigated structurally, these include ] pentahydrate (Na<sub>2</sub>HPO<sub>3</sub>·5H<sub>2</sub>O). (NH<sub>4</sub>)<sub>2</sub>HPO<sub>3</sub>·H<sub>2</sub>O, CuHPO<sub>3</sub>·H<sub>2</sub>O, SnHPO<sub>3</sub> and Al<sub>2</sub>(HPO<sub>3</sub>)<sub>3</sub>·4H<sub>2</sub>O.<ref>"Synthesis and crystal structures of aluminum and iron phosphites", D.M. Poojary, Y. Zhang, D.E. Cox, P.R. Rudolf, S. Cheng & A. Clearfield, ''J. Chem. Crystallogr.'' '''24''' (1994) 155–163</ref> The structure of {{chem|HPO|3|2−}} is approximately tetrahedral.<ref name = "Gordon">L. E. Gordon, W. T. A. Harrison. "Bis(melaminium) hydrogen phosphite tetrahydrate". ''Acta Crystallogr.'' '''59''' (2): o195–o197. {{doi|10.1107/S1600536803001247}}</ref><ref name = "Loub">"Crystal chemistry of inorganic phosphites", J. Loub, ''Acta Crystallogr.'' (1991), '''B47''', 468–473, {{doi|10.1107/S0108768191002380}}</ref>


{{chem|HPO|3|2−}} has a number of canonical resonance forms making it isoelectronic with ] ion, {{chem|HSO|3|−}}, which has a similar structure.<ref name = "Greenwood"/>
==Acid phosphites==
Acid or hydrogen phosphites (which the IUPAC recommends be called acid or hydrogen phosphonates), such as NH<sub>4</sub>HP(O)<sub>2</sub>OH, can be prepared from ], HP(O)(OH)<sub>2</sub>.<ref name = "Greenwood"/> Hydrogen bonding between anions leads to polymeric anionic structures. <ref name = "Loub"/> Recently some others, RbHPHO<sub>3</sub>, CsHPHO<sub>3</sub>, TlHPHO<sub>3</sub> have been prepared by reacting ] with the metal ]. These compounds contain a layer polymeric anion consisting of HPO<sub>3</sub> tetrahedra linked by hydrogen bonds. These layers are interleaved by layers of metal cations.<ref>{{cite journal
|author=Kosterina, E. V., Troyanov, S. I., Kemnitz, E. & Aslanov, L. A.
|title=Synthesis and Crystal Structure of Acid Phosphites RbH<sub>2</sub>PO<sub>3</sub>, CsH<sub>2</sub>PO<sub>3</sub>, and TlH<sub>2</sub>PO<sub>3</sub>
|journal=Russian Journal of Coordination Chemistry
|year=2001|volume=27|pages=458–462
|doi=10.1023/A:1011377229855}}</ref>


]
==Pyrophosphites==
Pyrophosphites (diphosphites) can be produced by gently heating acid phosphites under reduced pressure. They contain the ion, H<sub>2</sub>P<sub>2</sub>O<sub>5</sub><sup>2−</sup>which can be formulated <sup>2−</sup>.<ref name = "Greenwood"/><ref name = "Loub"/>


==Salts containing HP(O)<sub>2</sub>OH<sup>−</sup>==
==Naming of phosphite ions==
Acid or hydrogen phosphites are called hydrogenphosphonates or acid phosphites. IUPAC recommends the name hydrogenphosphonates). They are anions HP(O)<sub>2</sub>OH<sup>−</sup>. A typical derivative is the salt .<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref><ref name = "Loub"/> Many related salts are known, e.g., RbHPHO<sub>3</sub>, CsHPHO<sub>3</sub>, TlHPHO<sub>3</sub>. These salts are prepared by treating ] with the metal ]. These compounds contain a layer polymeric anion consisting of HPO<sub>3</sub> tetrahedra linked by hydrogen bonds. These layers are interleaved by layers of metal cations.<ref>{{cite journal
The traditional name for HPO<sub>3</sub><sup>2−</sup> is phosphite, and for HPO<sub>2</sub>(OH)<sup>−</sup> is hydrogenphosphite or acid phosphite. However IUPAC recommendations are that HPO<sub>3</sub><sup>2−</sup> is to be named hydrogenphosphite or phosphonate, HPO<sub>2</sub>(OH)<sup>−</sup> is to be named dihydrogenphosphite or hydrogenphosphonate and phosphite is reserved for the hypothetical PO<sub>3</sub><sup>3−</sup> ion. <ref name = "IUPAC inorganic"> NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 ed. N. G. Connelly et al. RSC Publishing http://www.chem.qmul.ac.uk/iupac/bioinorg/</ref>
| vauthors = Kosterina EV, Troyanov SI, Kemnitz E, Aslanov LA
| title=Synthesis and Crystal Structure of Acid Phosphites RbH<sub>2</sub>PO<sub>3</sub>, CsH<sub>2</sub>PO<sub>3</sub>, and TlH<sub>2</sub>PO<sub>3</sub>
| journal=Russian Journal of Coordination Chemistry
| year=2001|volume=27|pages=458–462
| doi=10.1023/A:1011377229855
| issue=7| s2cid=91297300
}}</ref>


Organic esters of hydrogen phosphites are anions with the formula HP(O)<sub>2</sub>OR<sup>−</sup> (R = organic group). One commercial example is the ] ] with the formula <sub>3</sub>Al.<ref>{{cite encyclopedia |author=Franz Müller |author2=Peter Ackermann |author3=Paul Margot |title=Fungicides, Agricultural, 2. Individual Fungicides|encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry|publisher=Wiley-VCH|place=Weinheim|year=2012|doi=10.1002/14356007.o12_o06|isbn=978-3-527-30673-2}}</ref>
==Synthesis of phosphite esters==

==Salts containing H<sub>2</sub>P<sub>2</sub>O<sub>5</sub><sup>2−</sup>, called diphosphites or pyrophosphites==
Pyrophosphites (diphosphites) can be produced by gently heating acid phosphites under reduced pressure. They contain the ion {{chem|H|2|P|2|O|5|2−}}, which can be formulated <sup>2−</sup>.<ref name = "Greenwood"/><ref name = "Loub"/>

==Parallels in arsenic chemistry==
In contrast to the paucity of evidence for {{chem|PO|3|3−}}, the corresponding arsenic ion, ortho-], {{chem|AsO|3|3−}} is known. An example is Ag<sub>3</sub>AsO<sub>3</sub> as well as the polymeric meta-arsenite {{chem|(AsO|2|−|)|''n''}}.<ref name = "Greenwood"/> The iso-electronic ] ion, {{chem|SO|3|2−}} is known from its salts.<ref name = "Greenwood"/>
<!--==Synthesis of phosphite esters==
]s called ]s (or sometimes just phosphites) have the formula (]O)<sub>3</sub>P. They are prepared by reacting ] (or ]) with an ] and a tertiary ]. ]s called ]s (or sometimes just phosphites) have the formula (]O)<sub>3</sub>P. They are prepared by reacting ] (or ]) with an ] and a tertiary ].


PCl<sub>3</sub> + 3 ROH + 3 R'<sub>3</sub>N → P(OR)<sub>3</sub> + 3R'<sub>3</sub>NHCl :PCl<sub>3</sub> + 3 ROH + 3 R′<sub>3</sub>N → P(OR)<sub>3</sub> + 3R′<sub>3</sub>NHCl-->


==Use in plants== ==Use as fungicides==
{{missing information|section|mechanism of antifungal/antiprotozoal action|date=March 2022}}
Inorganic phosphites have been applied to crops to combat fungus-like pathogens of the order ]s. The situation is confusing because of the similarity in name between phosphite and ] (a major plant ] and ] ingredient), and controversial because phosphites have sometimes been advertised as fertilizers, even though they are converted to phosphate too slowly to serve as a plant's main phosphorus source. Lemoynie<ref></ref> and others<ref>{{cite journal |last1=Thao |first1= |last2=Yamakawa |first2= |year=2008 |title= |journal=Soil Science and Plant Nutrition |volume=55 |issue= |pages=228–234 |publisher= |doi= |url= |accessdate= }}</ref> have described this complicated situation and noted that calling phosphites fertilizers avoided the regulatory complication and negative public perceptions that might have been incurred by registering them as fungicides.
Inorganic phosphites (containing {{chem|HPO|3|2−}}) have been applied to crops to combat fungus-like pathogens of the order ]s (water molds). The situation is confusing because of the similarity in name between phosphite and ] (a major plant ] and ] ingredient), and controversial because phosphites have sometimes been advertised as fertilizers, even though they are converted to phosphate too slowly to serve as a plant's main phosphorus source. In fact, phosphites may cause phytotoxicity when a plant is starved of phosphates.<ref name=Thao/> Lemoynie<ref></ref> and others have described this complicated situation and noted that calling phosphites fertilizers avoided the regulatory complication and negative public perceptions that might have been incurred by registering them as fungicides.<ref name=Thao>{{cite journal |last1=Thao |last2=Yamakawa |year=2008 |title=Phosphite (phosphorous acid): Fungicide, fertilizer or bio-stimulator? |journal=Soil Science and Plant Nutrition |volume=55 |issue=2 |pages=228–234 |doi= 10.1111/j.1747-0765.2009.00365.x|s2cid=95723306 |doi-access=free }}</ref>

A major form of inorganic phosphite used in agriculture is ]. This compound does serve as a potassium fertilizer.


==See also== ==See also==
* ] – {{chem|H|2|PO|2|−}}
* ] * ]
* ] - PR<sub>3</sub> * ] – PH<sub>3</sub> and the organic phosphines PR<sub>3</sub>
* ] - OPR<sub>3</sub> * ] – OPR<sub>3</sub>
* ] - P(OR)R<sub>2</sub> * ] – P(OR)R<sub>2</sub>
* ] - P(OR)<sub>2</sub>R * ] – P(OR)<sub>2</sub>R
* ] - OP(OR)R<sub>2</sub> * ] – OP(OR)R<sub>2</sub>
* ] - OP(OR)<sub>2</sub>R * ] – organic phosphonates OP(OR)<sub>2</sub>R
* ] - OP(OR)<sub>3</sub> * ] – {{chem|PO|4|3−}}
* ] – OP(OR)<sub>3</sub>


==Further reading== ==Further reading==
*{{cite book | title=The Chemistry of the Elements - Second Edition| author=A. Earnshaw, Norman Greenwood| year=1997| pages=513–514}} *{{cite book | title=The Chemistry of the Elements |edition=2nd|author1=A. Earnshaw |author2=Norman Greenwood | year=1997| pages=513–514}}


==References== ==References==
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Latest revision as of 09:06, 6 January 2025

Ion For phosphites of the type P(OR)3, see Phosphite ester.
Phosphite anion
Names
IUPAC name Phosphonate
Systematic IUPAC name Phosphite
Identifiers
CAS Number
3D model (JSmol)
ChEBI
ChemSpider
Gmelin Reference 1618
MeSH Phosphorite
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/O3P/c1-4(2)3/q-3Key: AQSJGOWTSHOLKH-UHFFFAOYSA-N
SMILES
  • hypervalent form: P()()=O
  • ionic form: ()()
Properties
Chemical formula HPO
3
Molar mass 79.9810 g mol
Related compounds
Other anions Phosphinite

Phosphonite

Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

A phosphite anion or phosphite in inorganic chemistry usually refers to but includes (). These anions are the conjugate bases of phosphorous acid (H3PO3). The corresponding salts, e.g. sodium phosphite (Na2HPO3) are reducing in character.

Nomenclature

The IUPAC recommended name for phosphorous acid is phosphonic acid. Correspondingly, the IUPAC-recommended name for the HPO
3 ion is phosphonate. In the US the IUPAC naming conventions for inorganic compounds are taught at high school, but not as a 'required' part of the curriculum. A well-known university-level textbook follows the IUPAC recommendations. In practice any reference to "phosphite" should be investigated to determine the naming convention being employed.

Salts containing HPO3, called phosphonates or phosphites

Structural formula of Na2HPO3. The anion has C3v symmetry.

From the commercial perspective, the most important phosphite salt is basic lead phosphite. Many salts containing the phosphite ion have been investigated structurally, these include sodium phosphite pentahydrate (Na2HPO3·5H2O). (NH4)2HPO3·H2O, CuHPO3·H2O, SnHPO3 and Al2(HPO3)3·4H2O. The structure of HPO
3 is approximately tetrahedral.

HPO
3 has a number of canonical resonance forms making it isoelectronic with bisulfite ion, HSO
3, which has a similar structure.

Salts containing HP(O)2OH

Acid or hydrogen phosphites are called hydrogenphosphonates or acid phosphites. IUPAC recommends the name hydrogenphosphonates). They are anions HP(O)2OH. A typical derivative is the salt . Many related salts are known, e.g., RbHPHO3, CsHPHO3, TlHPHO3. These salts are prepared by treating phosphorous acid with the metal carbonate. These compounds contain a layer polymeric anion consisting of HPO3 tetrahedra linked by hydrogen bonds. These layers are interleaved by layers of metal cations.

Organic esters of hydrogen phosphites are anions with the formula HP(O)2OR (R = organic group). One commercial example is the fungicide fosetyl-Al with the formula 3Al.

Salts containing H2P2O5, called diphosphites or pyrophosphites

Pyrophosphites (diphosphites) can be produced by gently heating acid phosphites under reduced pressure. They contain the ion H
2P
2O
5, which can be formulated .

Parallels in arsenic chemistry

In contrast to the paucity of evidence for PO
3, the corresponding arsenic ion, ortho-arsenite, AsO
3 is known. An example is Ag3AsO3 as well as the polymeric meta-arsenite (AsO
2)
n. The iso-electronic sulfite ion, SO
3 is known from its salts.

Use as fungicides

This section is missing information about mechanism of antifungal/antiprotozoal action. Please expand the section to include this information. Further details may exist on the talk page. (March 2022)

Inorganic phosphites (containing HPO
3) have been applied to crops to combat fungus-like pathogens of the order oomycetes (water molds). The situation is confusing because of the similarity in name between phosphite and phosphate (a major plant nutrient and fertilizer ingredient), and controversial because phosphites have sometimes been advertised as fertilizers, even though they are converted to phosphate too slowly to serve as a plant's main phosphorus source. In fact, phosphites may cause phytotoxicity when a plant is starved of phosphates. Lemoynie and others have described this complicated situation and noted that calling phosphites fertilizers avoided the regulatory complication and negative public perceptions that might have been incurred by registering them as fungicides.

A major form of inorganic phosphite used in agriculture is monopotassium phosphite. This compound does serve as a potassium fertilizer.

See also

Further reading

  • A. Earnshaw; Norman Greenwood (1997). The Chemistry of the Elements (2nd ed.). pp. 513–514.

References

  1. "Phosphorite - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information.
  2. Physical setting/ chemistry core curriculum, The University of the State of New York, The State Education Department, http://www.p12.nysed.gov/ciai/mst/pub/chemist.pdf Archived 2018-03-29 at the Wayback Machine
  3. Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
  4. "Synthesis and crystal structures of aluminum and iron phosphites", D.M. Poojary, Y. Zhang, D.E. Cox, P.R. Rudolf, S. Cheng & A. Clearfield, J. Chem. Crystallogr. 24 (1994) 155–163
  5. L. E. Gordon, W. T. A. Harrison. "Bis(melaminium) hydrogen phosphite tetrahydrate". Acta Crystallogr. 59 (2): o195–o197. doi:10.1107/S1600536803001247
  6. ^ "Crystal chemistry of inorganic phosphites", J. Loub, Acta Crystallogr. (1991), B47, 468–473, doi:10.1107/S0108768191002380
  7. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  8. Kosterina EV, Troyanov SI, Kemnitz E, Aslanov LA (2001). "Synthesis and Crystal Structure of Acid Phosphites RbH2PO3, CsH2PO3, and TlH2PO3". Russian Journal of Coordination Chemistry. 27 (7): 458–462. doi:10.1023/A:1011377229855. S2CID 91297300.
  9. Franz Müller; Peter Ackermann; Paul Margot (2012). "Fungicides, Agricultural, 2. Individual Fungicides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.o12_o06. ISBN 978-3-527-30673-2.
  10. ^ Thao; Yamakawa (2008). "Phosphite (phosphorous acid): Fungicide, fertilizer or bio-stimulator?". Soil Science and Plant Nutrition. 55 (2): 228–234. doi:10.1111/j.1747-0765.2009.00365.x. S2CID 95723306.
  11. "Phosphites and Phosphates: When Distributors and Growers alike could get confused!" by Jean-Pierre Leymonie. Courtesy of New Ag International, September 2007 edition.
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