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{{Short description|Ion}} |
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{{for|phosphites of the type P(OR)<sub>3</sub>|Phosphite ester}} |
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| ImageFile = Phosphite ion.svg |
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| verifiedrevid = 411474802 |
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| ImageFileL1 = Phosphite-ion-from-xtal-3D-balls.png |
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| ImageFile = |
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| ImageFileR1 = Phosphite-ion-from-xtal-3D-vdW.png |
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| IUPACName = phosphite |
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| IUPACName = Phosphonate |
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| Section1 = {{Chembox Identifiers |
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| Verifiedfields = changed |
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| SMILES = P()()}} |
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|Section2= {{Chembox Properties |
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| verifiedrevid = 415680520 |
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| Formula=PO<sub>3</sub><sup>3-</sup> |
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| 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> |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|changed|??}} |
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| CASNo = 15477-76-6 |
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| PubChem = 406 |
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| ChemSpiderID = 10449627 |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| MeSHName = Phosphorite |
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| ChEBI_Ref = {{ebicite|changed|EBI}} |
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| ChEBI = 16215 |
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| ChEMBL = |
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| ChEMBL_Ref = {{ebicite|changed|EBI}} |
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| Gmelin = 1618 |
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| KEGG = |
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| SMILES = P()()=O |
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| SMILES_Comment = hypervalent form |
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| SMILES1 = ()() |
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| SMILES1_Comment = ionic form |
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| StdInChI = 1S/O3P/c1-4(2)3/q-3 |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = AQSJGOWTSHOLKH-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| Section2 = {{Chembox Properties |
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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> |
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| Formula = {{chem|HPO|3|2−}} |
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| MolarMass = 79.9810 g mol<sup>−1</sup> |
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| Section3 = {{Chembox Related |
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| OtherAnions = ]<br /> |
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] |
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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. |
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==Nomenclature== |
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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. |
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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. |
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==Salts containing HPO<sub>3</sub><sup>2−</sup>, called phosphonates or phosphites== |
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The term phosphite is also used to mean ], an ] compound with the formula P(OR)<sub>3</sub>. |
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:]. The anion has C<sub>3v</sub> symmetry.]] |
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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> |
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{{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"/> |
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==Acid phosphites== |
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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 |
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|author=Kosterina, E. V., Troyanov, S. I., Kemnitz, E. & Aslanov, L. A. |
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|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> |
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|journal=Russian Journal of Coordination Chemistry |
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|year=2001|volume=27|pages=458–462 |
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|doi=10.1023/A:1011377229855}}</ref> |
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] |
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==Pyrophosphites== |
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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"/> |
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==Salts containing HP(O)<sub>2</sub>OH<sup>−</sup>== |
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==Naming of phosphite ions== |
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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 |
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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> |
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| vauthors = Kosterina EV, Troyanov SI, Kemnitz E, Aslanov LA |
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| 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> |
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| journal=Russian Journal of Coordination Chemistry |
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| year=2001|volume=27|pages=458–462 |
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| doi=10.1023/A:1011377229855 |
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| issue=7| s2cid=91297300 |
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}}</ref> |
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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> |
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==Synthesis of phosphite esters== |
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==Salts containing H<sub>2</sub>P<sub>2</sub>O<sub>5</sub><sup>2−</sup>, called diphosphites or pyrophosphites== |
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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"/> |
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==Parallels in arsenic chemistry== |
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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"/> |
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<!--==Synthesis of phosphite esters== |
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]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 ]. |
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]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 ]. |
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PCl<sub>3</sub> + 3 ROH + 3 R'<sub>3</sub>N → P(OR)<sub>3</sub> + 3R'<sub>3</sub>NHCl |
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:PCl<sub>3</sub> + 3 ROH + 3 R′<sub>3</sub>N → P(OR)<sub>3</sub> + 3R′<sub>3</sub>NHCl--> |
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==Use in plants== |
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==Use as fungicides== |
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{{missing information|section|mechanism of antifungal/antiprotozoal action|date=March 2022}} |
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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. |
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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> |
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A major form of inorganic phosphite used in agriculture is ]. This compound does serve as a potassium fertilizer. |
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==See also== |
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==See also== |
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* ] – {{chem|H|2|PO|2|−}} |
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* ] |
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* ] |
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* ] - PR<sub>3</sub> |
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* ] – PH<sub>3</sub> and the organic phosphines PR<sub>3</sub> |
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* ] - OPR<sub>3</sub> |
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* ] – OPR<sub>3</sub> |
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* ] - P(OR)R<sub>2</sub> |
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* ] – P(OR)R<sub>2</sub> |
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* ] - P(OR)<sub>2</sub>R |
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* ] – P(OR)<sub>2</sub>R |
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* ] - OP(OR)R<sub>2</sub> |
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* ] – OP(OR)R<sub>2</sub> |
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* ] - OP(OR)<sub>2</sub>R |
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* ] – organic phosphonates OP(OR)<sub>2</sub>R |
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* ] - OP(OR)<sub>3</sub> |
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* ] – {{chem|PO|4|3−}} |
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* ] – OP(OR)<sub>3</sub> |
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==Further reading== |
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==Further reading== |
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*{{cite book | title=The Chemistry of the Elements - Second Edition| author=A. Earnshaw, Norman Greenwood| year=1997| pages=513–514}} |
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*{{cite book | title=The Chemistry of the Elements |edition=2nd|author1=A. Earnshaw |author2=Norman Greenwood | year=1997| pages=513–514}} |
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==References== |
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==References== |
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