Phosphorine

Phosphorine
Names
	Preferred IUPAC name Phosphinine
	Other names Phosphabenzene
Identifiers
CAS Number	289-68-9 [PubChem];
3D model (JSmol)	Interactive image;
ChemSpider	109668 ;
MeSH	Phosphinine
PubChem CID	123046;
	InChI InChI=1S/C5H5P/c1-2-4-6-5-3-1/h1-5H Key: UNQNIRQQBJCMQR-UHFFFAOYSA-N ; InChI=1/C5H5P/c1-2-4-6-5-3-1/h1-5H Key: UNQNIRQQBJCMQR-UHFFFAOYAZ;
	SMILES C1=CC=PC=C1;
Properties
Chemical formula	C5H5P
Molar mass	96.069 g·mol−1
Related compounds
Related -ines	Arsabenzene; Pyridine; Silabenzene
Related compounds	Phosphole
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Phosphorine (IUPAC name: phosphinine) is a heavier 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^[2] but is otherwise stable when handled using air-free techniques (however, substituted derivatives can often be handled under air without risk of decomposition).^[3]^[4] 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

The first phosphorine to be isolated is 2,4,6-triphenylphosphorine. It was synthesized by Gottfried Märkl in 1966 by condensation of the corresponding pyrylium salt and phosphine or its equivalent ( P(CH₂OH)₃ and P(SiMe₃)₃).^[3]

500px|Synthesis of Triphenylphosphabenzene

The (unsubstituted) parent phosphorine was reported by Arthur J. Ashe III in 1971.^[2]^[5] Ring-opening approaches have been developed from phospholes.^[6]

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 electronegativities of phosphorus (2.1) and carbon (2.5). The P-C bond length is 173 pm and the C-C bond lengths center around 140 pm and show little variation.^[7]

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 pK_a's of C₅H₅PH⁺ and C₅H₅NH⁺ are respectively -16.1 and 5.2.^[6] Methyl lithium adds to phosphorus in phosphorine whereas it adds to the 2-position of pyridine.^[8]

Phosphorine undergoes electrophilic substitution reactions like ordinary aromatic compounds: bromination, acylation, and so on.

Coordination chemistry

Coordination complexes bearing phosphorine as a [ligand] are known. Phosphorines can bind to metals through phosphorus center. Complexes of the diphospha analogue of 2,2'-bipyridine are known. Phosphorines also form pi-complexes, illustrated by V(η⁶-C₅H₅P)₂.^[6]

References

↑ "CHAPTER P-1. General Principles, Rules, and Conventions". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 47. doi:10.1039/9781849733069-00001. ISBN 978-0-85404-182-4.
↑ ^2.0 ^2.1 Ashe, A. J. (1971). "Phosphabenzene and Arsabenzene". Journal of the American Chemical Society 93 (13): 3293–3295. doi:10.1021/ja00742a038.
↑ ^3.0 ^3.1 G. Märkl, 2,4,6-Triphenylphosphabenzol in Angewandte Chemie 78, 907–908 (1966)
↑ Newland, R. J.; Wyatt, M. F.; Wingad, R. L.; Mansell, S. M. (2017). "A ruthenium( ii ) bis(phosphinophosphinine) complex as a precatalyst for transfer-hydrogenation and hydrogen-borrowing reactions" (in en). Dalton Transactions 46 (19): 6172–6176. doi:10.1039/C7DT01022B. ISSN 1477-9226. PMID 28436519.
↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 544. ISBN 978-0-08-037941-8.
↑ ^6.0 ^6.1 ^6.2 François Mathey "Phosphorus Heterocycles" in Modern Heterocyclic Chemistry, First Edition, edited by Julio Alvarez-Builla, Juan Jose Vaquero, José Barluenga, Wiley-VCH, Weinheim, 2011. doi:10.1002/9783527637737.ch23.
↑ László Nyulászi "Aromaticity of Phosphorus Heterocycles" Chem. Rev., 2001, volume 101, pp 1229–1246. doi:10.1021/cr990321x
↑ 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

Quin, L. D. (2000). A Guide to Organophosphorus Chemistry. Wiley-Interscience. ISBN 978-0-471-31824-8.

External links

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[iupac2013-1] "CHAPTER P-1. General Principles, Rules, and Conventions". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 47. doi:10.1039/9781849733069-00001. ISBN 978-0-85404-182-4.

[Ashe-2] 2.0 ^2.1 Ashe, A. J. (1971). "Phosphabenzene and Arsabenzene". Journal of the American Chemical Society 93 (13): 3293–3295. doi:10.1021/ja00742a038.

[:0-3] 3.0 ^3.1 G. Märkl, 2,4,6-Triphenylphosphabenzol in Angewandte Chemie 78, 907–908 (1966)

[4] Newland, R. J.; Wyatt, M. F.; Wingad, R. L.; Mansell, S. M. (2017). "A ruthenium( ii ) bis(phosphinophosphinine) complex as a precatalyst for transfer-hydrogenation and hydrogen-borrowing reactions" (in en). Dalton Transactions 46 (19): 6172–6176. doi:10.1039/C7DT01022B. ISSN 1477-9226. PMID 28436519.

[5] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 544. ISBN 978-0-08-037941-8.

[Mathey-6] 6.0 ^6.1 ^6.2 François Mathey "Phosphorus Heterocycles" in Modern Heterocyclic Chemistry, First Edition, edited by Julio Alvarez-Builla, Juan Jose Vaquero, José Barluenga, Wiley-VCH, Weinheim, 2011. doi:10.1002/9783527637737.ch23.

[7] László Nyulászi "Aromaticity of Phosphorus Heterocycles" Chem. Rev., 2001, volume 101, pp 1229–1246. doi:10.1021/cr990321x

[8] 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

Phosphorine

Contents

History

Structure, bonding, and properties

Coordination chemistry

See also

References

External links