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{{chembox |
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| verifiedrevid = 268956601 |
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|verifiedrevid = 414727061 |
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| Name = Phenyllithium |
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| ImageFile = Phenyllithium.svg |
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|ImageFile1 = Phenyllithium.svg |
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|ImageFile2 = Phenyllithium-chain-from-xtal-Mercury-3D-balls.png |
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| ImageSize = 150px |
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|ImageFile_Ref = {{chemboximage|correct|??}} |
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| IUPACName = Phenyllithium |
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|ImageName1 = Kekulé, skeletal formula of phenyllithium |
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| OtherNames = PhLi, phenyl lithium |
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|SystematicName = Phenyllithium<ref>{{Cite web | title = phenyllithium (CHEBI:51470) | url = https://www.ebi.ac.uk/chebi/searchId.do?chebiId=51470 | work = Chemical Entities of Biological Interest (ChEBI)| publisher = European Bioinformatics Institute | accessdate = 2013-06-01 | location = Cambridge, UK | date = 2009-01-22 | at = Main}}</ref> |
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| Section1 = {{Chembox Identifiers |
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|OtherNames = Lithiobenzene<ref>Typically used to describe substituted derivatives. See, e.g., Katsutoshi Kobayashi; Soichi Sato; Horn, Ernst; Naomichi Furukawa (1998), "First isolation and characterization of sulfenium cation salts stabilized by the coordination of two nitrogen atoms," ''Tetrahedron Letters'', '''39''': 17, pp. 2593-2596. ISSN 0040-4039. DOI .</ref> |
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| CASNo = 591-51-5 |
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|Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|Abbreviations = LiPh, PhLi |
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| PubChem = 24845894 |
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|CASNo = 591-51-5 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| RTECS = |
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| EINECS = |
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|PubChem = 637932 |
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|ChemSpiderID = 10254416 |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|EINECS = 209-720-1 |
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| Section2 = {{Chembox Properties |
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|MeSHName = phenyllithium |
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| Formula = C<sub>6</sub>H<sub>5</sub>Li |
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|ChEBI = 51470 |
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| MolarMass = 84.05 g/mol |
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|ChEBI_Ref = {{ebicite|correct|EBI}} |
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| Appearance = Colorless crystals, solutions in cyclohexane/ether are dark brown, solutions in THF are reddish |
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|Beilstein = 506502 |
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| Density = 0.828 g/cm<sup>3</sup> |
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|Gmelin = 2849 |
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| Solubility = Severe reaction with water |
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|SMILES = c1ccccc1 |
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| SolubleOther = |
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|StdInChI = 1S/C6H5.Li/c1-2-4-6-5-3-1;/h1-5H; |
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| MeltingPt = |
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|StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| BoilingPt = 140-143 °C |
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|StdInChIKey = NHKJPPKXDNZFBJ-UHFFFAOYSA-N |
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| pKa = |
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|StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| Section3 = {{Chembox Structure |
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|Section2 = {{Chembox Properties |
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|Formula = {{Chem|LiC|6|H|5}} |
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| MolShape = |
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|MolarMass = 84.045 g mol<sup>−1</sup> |
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| Dipole = |
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|Appearance = Colorless crystals |
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|Density = 828 mg cm<sup>−3</sup> |
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| Section4 = {{Chembox Thermochemistry |
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|Solubility = Reacts |
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| DeltaHf = |
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|BoilingPtC = 140 to 143 |
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| Entropy = |
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|Section3 = {{Chembox Thermochemistry |
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| HeatCapacity = |
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|DeltaHf = 48.3-52.5 kJ mol<sup>−1</sup> |
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| Section7 = {{Chembox Hazards |
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|Section4 = {{Chembox Hazards |
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| ExternalMSDS = |
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|ExternalSDS = |
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|GHSPictograms = {{GHS02}}{{GHS05}}{{GHS07}} |
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| EUClass = |
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|GHSSignalWord = Danger |
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| RPhrases = {{R14}} {{R17}} {{R23}} {{R24}} {{R25}} {{R46}} {{R48}} |
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|HPhrases = {{H-phrases|226|250|261|302|312|314|332}} |
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| SPhrases = {{S8}} {{S9}} {{S16}} {{S26}} {{S30}} {{S46}} {{S37}} {{S39}} {{S45}} |
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|PPhrases = {{P-phrases|210|222|231+232|233|240|241|242|243|260|261|264|270|271|280|301+312|301+330+331|302+334|302+352|303+361+353|304+312|304+340|305+351+338|310|312|321|322|330|363|370+378|402+404|403+235|405|422|501}} |
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| NFPA-F = |
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|Section5 = {{Chembox Related |
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| NFPA-R = |
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|OtherCompounds = ], ], ] |
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| Section8 = {{Chembox Related |
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'''Phenyllithium''' is an ] agent with the empirical formula C<sub>6</sub>H<sub>5</sub>Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for ] for introducing phenyl groups in organic syntheses.<ref>Wietelmann, U.; Bauer, R.J. “Lithium and Lithium Compounds“ in ''Ullmann’s Encyclopedia of Industrial Chemistry'', 2002, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a15}}</ref> Crystalline phenyllithium is colorless; however, solutions of phenyllithium are various shades of brown or red depending on the solvent used and the impurities present in the solute.<ref>Gilman, H.; Zoellner, E.A.; Selby, W.M. An Improved Procedure for the Preparation of Organolithium Compounds. ''J. Am. Chem. Soc''. 1932 '''54''' (5), 1957-1962. {{DOI|10.1021/ja01344a033}}</ref> |
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'''Phenyllithium''' is an ] agent with the empirical formula C<sub>6</sub>H<sub>5</sub>Li. It is most commonly used as a metalating agent in organic syntheses and a substitute for ] for introducing phenyl groups in organic syntheses.<ref>{{ Ullmann | author = Wietelmann, U. | author2 = Bauer, R. J. | contribution = Lithium and Lithium Compounds | doi = 10.1002/14356007.a15_393 | contribution-url = http://onlinelibrary.wiley.com/doi/10.1002/14356007.a15_393/abstract}}</ref> Crystalline phenyllithium is colorless; however, solutions of phenyllithium are various shades of brown or red depending on the solvent used and the impurities present in the solute.<ref>{{cite journal |author1=Gilman, H. |author2=Zoellner, E. A. |author3=Selby, W. M. | title = An Improved Procedure for the Preparation of Organolithium Compounds | journal = ] | year = 1932 | volume = 54 | issue = 5 | pages = 1957–1962 | doi = 10.1021/ja01344a033}}</ref> |
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==Structure and properties== |
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Phenyllithium is an ] compound that forms monoclinic crystals. Solid phenyllithium can be described as consisting of dimeric Li<sub>2</sub>Ph<sub>2</sub> subunits. The Li atoms and the ipso carbons of the phenyl rings form a planar four-membered ring. The plane of the phenyl groups are perpendicular to the plane of this Li<sub>2</sub>C<sub>2</sub> ring. Additional intermolecular bonding occurs between these phenyllithium dimers and the π-electrons of the phenyl groups in the adjacent dimers.<ref>Hope, H.; Power, P.P. Isolation and Crystal Structures of the Halide-Free and Halide-Rich Phenyllithium Etherate Complexes and . ''J. Am. Chem. Soc.'' 1983 '''105''' (16), 5320-5324. {{DOI|10.1021/ja00354a022}}</ref> |
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In solution, it takes a variety of structures dependent on the organic solvent. In ], it equilibrates between monomer and dimer states. In ether, as it is commonly sold, phenyllithium exists as a tetramer. Four Li atoms and four ipso carbon centers occupy alternating vertices of a distorted cube. Phenyl groups are at the faces of the tetrahedron and bind to three of the nearest Li atoms. |
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The C-Li bond lengths are an average of 2.33 Å. An ether molecule binds to each of the Li sites through its oxygen atom. In the presence of LiBr, a byproduct of directly reacting lithium with a phenyl halide, the complex instead becomes [(PhLi • Et<sub>2</sub>O)<sub>3</sub> • LiBr). The Li atom of LiBr occupies one of the lithium sites in the cubane-like frame, and Br atom sits in an adjacent carbon site. |
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==Preparation== |
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==Preparation== |
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Phenyllithium was first produced by the reaction of lithium metal with ]:<ref>Green, D.P.; Zuev, D. “Phenyllithium” in Encyclopedia of Reagents for Organic Synthesis, 2008, Wiley and Sons. {{DOI|10.1002/047084289X.rp076.pub2}}</ref> |
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Phenyllithium was first produced by the reaction of lithium metal with ]:<ref>{{ cite encyclopedia |author1=Green, D. P. |author2=Zuev, D. | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | year = 2008 | publisher = Wiley and Sons | doi = 10.1002/047084289X.rp076.pub2 | chapter-url = http://onlinelibrary.wiley.com/o/eros/articles/rp076/frame.html |isbn=978-0471936237 |chapter=Phenyllithium }}</ref> |
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:(C<sub>6</sub>Η<sub>5</sub>)<sub>2</sub>Ηg + 2Li → 2C<sub>6</sub>Η<sub>5</sub>Li + Ηg |
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Reaction of a phenyl halide with lithium metal produces phenyllithium: |
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:(C<sub>6</sub>Η<sub>5</sub>)<sub>2</sub>Ηg + 2Li → 2C<sub>6</sub>Η<sub>5</sub>Li + Ηg |
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:X-Ph + 2Li → Ph-Li + LiX |
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The synthesis was improved soon afterward by directly reacting ] with phenyl halides.<ref>Dinnebier, R.E.; Behrens, U.; Olbrich, F. Lewis Base-Free Phenyllithium: Determination of the Solid-State Structure by Synchrotron Powder Diffraction. ''J. Am. Chem. Soc.'' 1998 '''120''' (7), 1430-1433. {{DOI|10.1021/ja972816e}}</ref> |
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:C<sub>6</sub>H<sub>5</sub>X + 2Li → C<sub>6</sub>H<sub>5</sub>Li + LiX |
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Phenyllithium can also be synthesized with a metal-halogen exchange reaction: |
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Phenyllithium can also be synthesized with a metal-halogen exchange reaction: |
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:n-BuLi + X-Ph → n-BuX + Ph-Li |
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:n-BuLi + X-Ph → n-BuX + Ph-Li |
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The predominant method of producing phenyllithium today are the latter two syntheses. |
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The predominant method of producing phenyllithium today are the latter two syntheses. |
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==Reactions== |
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==Reactions== |
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The primary use of PhLi is to facilitate formation of carbon-carbon bonds by nucleophilic addition and substitution reactions: |
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:PhLi + R<sub>2</sub>C=O → PhR<sub>2</sub>COLi |
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] is prepared by the reaction of phenyl lithium with pyridine, a process that entails an addition-elimination pathway:<ref>Evans, J. C. W.; Allen, C. F. H. "2-Phenylpyridine" Organic Syntheses (1938), vol. 18, p. 70 {{doi|10.15227/orgsyn.018.0070}}</ref> |
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:C<sub>6</sub>H<sub>5</sub>Li + C<sub>5</sub>H<sub>5</sub>N → C<sub>6</sub>H<sub>5</sub>-C<sub>5</sub>H<sub>4</sub>N + LiH |
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==Structure and properties== |
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] |
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Phenyllithium is an ] compound that forms monoclinic crystals. Solid phenyl­lithium can be described as consisting of dimeric Li<sub>2</sub>Ph<sub>2</sub> subunits. The Li atoms and the '']'' carbons of the phenyl rings form a planar four-membered ring. The plane of the phenyl groups are perpendicular to the plane of this Li<sub>2</sub>C<sub>2</sub> ring. Additional strong inter­molecular bonding occurs between these phenyllithium dimers and the π-electrons of the phenyl groups in the adjacent dimers, resulting in an infinite polymeric ladder structure.<ref>{{Cite journal | last1 = Dinnebier | first1 = R. E. | last2 = Behrens | first2 = U. | last3 = Olbrich | first3 = F. | title = Lewis Base-Free Phenyllithium: Determination of the Solid-State Structure by Synchrotron Powder Diffraction | journal = ] | year = 1998 | volume = 120 | issue = 7 | pages = 1430–1433 | doi = 10.1021/ja972816e}}</ref> |
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] groups omitted for clarity) of a phenyl­lithium etherate tetramer crystal]] |
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The primary use of PhLi is to facilitate formation of carbon-carbon single bonds by nucleophilic addition and substitution reactions: |
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In solution, it takes a variety of structures dependent on the organic solvent. In ], it equilibrates between monomer and dimer states. In ether, as it is commonly sold, phenyllithium exists as a tetramer. Four Li atoms and four ipso carbon centers occupy alter­nating vertices of a distorted cube. Phenyl groups are at the faces of the tetrahedron and bind to three of the nearest Li atoms. |
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The C–Li bond lengths are an average of 2.33 Å. An ether molecule binds to each of the Li sites through its oxygen atom. In the presence of LiBr, a byproduct of directly reacting lithium with a phenyl halide, the complex instead becomes . The Li atom of LiBr occupies one of the lithium sites in the ] and Br atom sits in an adjacent carbon site.<ref>{{cite journal |author1=Hope, H. |author2=Power, P. P. | title = Isolation and Crystal Structures of the Halide-Free and Halide-Rich Phenyllithium Etherate Complexes and | journal = Journal of the American Chemical Society | year = 1983 | volume = 105 | issue = 16 | pages = 5320–5324 | doi = 10.1021/ja00354a022}}</ref> |
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:PhLi + R<sub>2</sub>C=O → PhR<sub>2</sub>COLi |
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==References== |
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==References== |
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{{reflist}} |
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{{Reflist}} |
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{{Lithium compounds}} |
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] |
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