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{{distinguish|phosphine}}
 
{{Chembox
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|ImageSizeR1 = 121
|ImageNameR1 = Aromatic ball and stick model of phosphorine
|PIN = Phosphinine<ref name=iupac2013>{{bluebook2013}} p.&nbsp;47.</ref>
|PIN = Phosphinine<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = [[Royal Society of Chemistry|The Royal Society of Chemistry]] | date = 2014 | location = Cambridge | page = 47 | doi = 10.1039/9781849733069-00001 | isbn = 978-0-85404-182-4| chapter = CHAPTER P-1. General Principles, Rules, and Conventions}}</ref>
|OtherNames = Phosphabenzene
|Section1 = {{Chembox Identifiers
|CASNo = 289-68-9
|CASNo_Ref = {{cascite|correct|PubChem}}
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = A8TY55D4JJ
|PubChem = 123046
|ChemSpiderID = 109668
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| Section3 = {{Chembox Related
| OtherFunction_label = -ines
| OtherFunction = {{ubl|[[Pyridine]]|[[Arsabenzene]]<br />|[[Silabenzene]]}}
[[Pyridine]]<br />
[[Silabenzene]]
|OtherCompounds = [[Phosphole]]
}}
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'''Phosphorine''' ([[IUPAC]] name: '''phosphinine''') is a heavier [[Chemical element|element]] analog of [[pyridine]], containing a [[phosphorus]] atom instead of an [[aza-]] moiety. It is also called '''phosphabenzene''' and belongs to the [[phosphaalkene]] class. It is a colorless liquid that is mainly of interest in research.
 
Phosphorine is an air-sensitive oil<ref name="Ashe" /> but is otherwise stable when handled using [[air-free technique]]s (however, substituted derivatives can often be handled under air without risk of decomposition).<ref name=":0" /><ref>{{Cite journal|lastlast1=Newland|firstfirst1=R. J.|last2=Wyatt|first2=M. F.|last3=Wingad|first3=R. L.|last4=Mansell|first4=S. M.|date=2017|title=A ruthenium( ii II) bis(phosphinophosphinine) complex as a precatalyst for transfer-hydrogenation and hydrogen-borrowing reactions|journal=Dalton Transactions|language=en|volume=46|issue=19|pages=6172–6176|doi=10.1039/C7DT01022B|pmid=28436519|issn=1477-9226|doi-access=free|hdl=1983/8ceafa01-697c-4055-bd9f-3bfcb60d93f2|hdl-access=free}}</ref> In contrast, [[silabenzene]], a related heavy-element analogue of benzene, is not only air- and moisture-sensitive but also thermally unstable without extensive steric protection.
 
==History==
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==Structure, bonding, and properties==
Structural studies by electron diffraction reveal that phosphorine is a planar [[aromatic]] compound with 88% of aromaticity of that of [[benzene]]. Potentially relevant to its high aromaticity are the well matched [[electronegativity|electronegativities]] of phosphorus (2.1) and [[carbon]] (2.5). The P-CP–C [[bond length]] is 173 &nbsp;[[picometer|pm]] and the C-CC–C bond lengths center around 140 &nbsp;pm and show little variation.<ref>László Nyulászi "Aromaticity of Phosphorus Heterocycles" Chem. Rev., 2001, volume 101, pp 1229–1246. {{DOIdoi|10.1021/cr990321x}}</ref>
{|style="margin: 1em auto 1em auto;"
|[[File:Bond lengths of group 15 heterobenzenes and benzene.svg|center|thumb|620px|Bond lengths and angles of benzene, [[pyridine]], phosphorine, [[arsabenzene]], [[stibabenzene]] and [[bismabenzene]]]]
|}
 
Although phosphorine and [[pyridine]] are structurally similar, phosphorines are far less basic. The pKp''K''<sub>a</sub>'s of C<sub>5</sub>H<sub>5</sub>PH<sup>+</sup> and C<sub>5</sub>H<sub>5</sub>NH<sup>+</sup> are respectively -16−16.1 and +5.2.<ref name=Mathey>François MatheyThe "PhosphorusP-oxides Heterocycles"are inextremely Modern Heterocyclic Chemistryunstable, Firstrapidly Edition,adding editednucleophiles byto Julioa Alvarez-Builla,species Juantetracoordinate Joseat Vaquero,phosphorus. José Barluenga,Strongly Wiley-VCH,backbonding Weinheim,Lewis 2011.acids {{DOI|10(e.1002/9783527637737g.ch23}}.</ref> [[Methyltungsten lithiumpentacarbonyl]]) addscan tostabilize phosphorusa in[[dative phosphorinebond]] whereasfrom it adds to the 2-position of pyridinephosphorus.<ref name=Mathey>Ashe IIIMathey, ArthurFrançois J(2011).; Smith, Timothy W."Phosphorus Heterocycles"The reactionin of''Modern phosphabenzeneHeterocyclic Chemistry'', arsabenzene1st anded., stibabenzeneedited withby methyllithium."Álvarez-Builla, TetrahedronJulio; Letters 1977José&nbsp;Vaquero, volumeJuan; 18and Barluenga, ppJosé. 407 Weinheim: Wiley-410VCH. §23.3. {{DOIdoi|10.10161002/S0040-4039(01)92651-69783527637737.ch23}}.</ref>
 
Both [[electrophile]]s and strong, hard [[nucleophile]]s preferentially attack at phosphorus, but the ring aromaticity is sufficiently weak that the result is an [[addition reaction]], and not aromatic substitution.<ref name=Mathey/> Thus for example [[methyllithium]] adds to phosphorus in phosphorine whereas it adds to the 2-position of pyridine.<ref>Ashe III, Arthur J.; Smith, Timothy W. "The reaction of phosphabenzene, arsabenzene and stibabenzene with methyllithium." Tetrahedron Letters 1977, volume 18, pp. 407–410. {{doi|10.1016/S0040-4039(01)92651-6}}</ref> Halophosphorines do undergo noble-metal- or [[zirconocene]]-catalyzed substitution, and λ<sup>5</sup>-phosphorines exhibit [[electrophilic aromatic substitution|a much more traditional substitution chemistry]].<ref name=Mathey/>
 
Unlike [[arsabenzene]], phosphorine rarely participates in [[Diels-Alder]]-type cycloadditions; when it does, the coupling partner must be an extremely electron-poor alkyne. Phosphorine ''complexes'' are tolerable Diels-Alder reactants.<ref name=Mathey/>
Phosphorine undergoes electrophilic substitution reactions like ordinary [[aromatic]] compounds: [[bromination]], [[acylation]], and so on.
 
===Coordination chemistry===
[[Coordination complex]]es bearing phosphorine as a [[ligand]] are known. Phosphorines can bind to metals through phosphorus center. Complexes of the diphospha analogue of [[2,2'2′-bipyridine]] are known. Phosphorines also form pi-complexes, illustrated by V(''η''<sup>6</sup>-C<sub>5</sub>H<sub>5</sub>P)<sub>2</sub>.<ref name=Mathey/>
 
== See also ==
* 6Six-membered aromatic rings with one carbon replaced by an element from another group: [[borabenzene]], [[silabenzene]], [[germabenzene]], [[stannabenzene]], [[pyridine]], phosphorine, [[arsabenzene]], [[stibabenzene]], [[bismabenzene]], [[pyrylium]], [[thiopyrylium]], [[selenopyrylium]], [[telluropyrylium]]
 
== References ==
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[[Category:Phosphorus heterocycles]]
[[Category:Six-membered rings]]
[[Category:Substances discovered in the 1970s]]
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