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{{chembox |
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| verifiedrevid = 396484592 |
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|verifiedrevid = 437791930 |
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| ImageFile = Diphenylphosphine.svg |
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|ImageFile = Diphenylphosphine.svg |
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| ImageName = Ball-and-stick model |
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| ImageFile1 = Diphenylphosphine-3D-balls.png |
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|ImageName = Ball-and-stick model |
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|ImageFile1 = Diphenylphosphine-3D-balls.png |
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| ImageName1 = Ball-and-stick model |
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|ImageName1 = Ball-and-stick model |
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|ImageFile2 = Diphenylphosphine-3D-vdW.png |
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| IUPACName= diphenylphosphane |
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|PIN = Diphenylphosphane |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 63209 |
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|ChemSpiderID = 63209 |
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| InChI = 1/C12H11P/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12/h1-10,13H |
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|InChI = 1/C12H11P/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12/h1-10,13H |
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| SMILES = c2c(Pc1ccccc1)cccc2 |
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|SMILES = c2c(Pc1ccccc1)cccc2 |
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| InChIKey = GPAYUJZHTULNBE-UHFFFAOYAN |
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|InChIKey = GPAYUJZHTULNBE-UHFFFAOYAN |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C12H11P/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12/h1-10,13H |
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|StdInChI = 1S/C12H11P/c1-3-7-11(8-4-1)13-12-9-5-2-6-10-12/h1-10,13H |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = GPAYUJZHTULNBE-UHFFFAOYSA-N |
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|StdInChIKey = GPAYUJZHTULNBE-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 829-85-6 |
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|CASNo = 829-85-6 |
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|PubChem = 70017 |
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| Section2 = {{Chembox Properties |
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|EC_number = 212-591-4 |
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| Formula = C<sub>12</sub>H<sub>11</sub>P |
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|UNII = F9B5T7O7ZY |
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| MolarMass = 186.19 g/mol |
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| Appearance = colorless liquid |
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| Density = 1.07 g/cm<sup>3</sup>, liquid |
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| Solubility = Insoluble |
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| BoilingPt = 280 °C (553 K) |
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| Section3 = {{Chembox Hazards |
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| RPhrases = 17-36/37/38 |
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| SPhrases = 26-36 |
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|Section2={{Chembox Properties |
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'''Diphenylphosphine''', also known as diphenylphosphane, is ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>PH. This foul smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as ]. |
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|Formula = C<sub>12</sub>H<sub>11</sub>P |
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|MolarMass = 186.19 g/mol |
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|Appearance = colorless liquid |
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|Density = 1.07 g/cm<sup>3</sup>, liquid |
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|Solubility = Insoluble |
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|BoilingPtC = 280 |
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}} |
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|Section3={{Chembox Hazards |
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|GHSPictograms = {{GHS02}}{{GHS07}} |
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|GHSSignalWord = Danger |
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|HPhrases = {{H-phrases|250|315|319|335}} |
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|PPhrases = {{P-phrases|210|222|261|264|271|280|302+334|302+352|304+340|305+351+338|312|321|332+313|337+313|362|370+378|403+233|405|422|501}} |
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|ExternalSDS = |
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'''Diphenylphosphine''', also known as diphenylphosphane, is an ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>PH. This foul-smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as ]. |
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==Synthesis== |
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==Synthesis== |
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Diphenylphosphine can be prepared cheaply from ].<ref>{{cite journal | author = Wittenberg, D.; ] | title = Lithium Cleavages of Triphenyl Derivatives of Some Group Vb Elements in Tetrahydrofuran | journal = ] | year = 1958 | volume = 23 | pages = 1063–1065 | doi = 10.1021/jo01101a613}}</ref> |
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Diphenylphosphine can be prepared from ] by reduction to ], which can be protonated to give the title compound:<ref>{{cite book|title=Inorganic Syntheses |author=V. D. Bianco |author2=S. Doronzo|chapter=Diphenylphosphine |year=1976|volume=16|pages=161–188|doi=10.1002/9780470132470.ch43|isbn=9780470132470}}</ref> |
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:PPh<sub>3</sub> + 2 Li → LiPPh<sub>2</sub> + LiPh |
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:PPh<sub>3</sub> + 2 Li → LiPPh<sub>2</sub> + LiPh |
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:LiPPh<sub>2</sub> + H<sub>2</sub>O → Ph<sub>2</sub>PH + LiOH |
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:LiPPh<sub>2</sub> + H<sub>2</sub>O → Ph<sub>2</sub>PH + LiOH |
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==Uses and reactions== |
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==Uses and reactions== |
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In the laboratory, diphenylphosphine is a common intermediate. It readily deprotonated to give diphenylphosphide derivatives:<ref name = piotrowski> Piotrowski, D. W. “Diphenylphosphine” Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons: New York, 2001. {{DOI|10.1002/047084289X.rd427}}.</ref> |
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In the laboratory, diphenylphosphine is a common intermediate. It can be deprotonated to give diphenylphosphide derivatives:<ref name = piotrowski>{{cite encyclopedia | author = Piotrowski, D. W. | title = Diphenylphosphine | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | publisher = John Wiley & Sons | location = New York | year = 2001 | doi = 10.1002/047084289X.rd427 | isbn = 0471936235}}</ref> |
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:Ph<sub>2</sub>PH + <sup>n</sup>BuLi → Ph<sub>2</sub>PLi + <sup>n</sup>BuH |
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:Ph<sub>2</sub>PH + <sup>n</sup>BuLi → Ph<sub>2</sub>PLi + <sup>n</sup>BuH |
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The preparation of phosphine ]s, ], and ]s are commonly accomplished by alkylating diphenylphosphine. The hydrogen atom connected to phosphorus undergoes Michael-like addition to activated alkenes, providing products with which to produce phosphine ligands such as ] (Ph<sub>2</sub>PC<sub>2</sub>H<sub>4</sub>PPh<sub>2</sub>). Diphenylphosphine and especially diphenylphosphide derivatives are nucleophiles, so they add to carbon – heteroatom double bonds.<ref name = piotrowski/> For example, in the presence of concentrated hydrochloric acid at 100 °C, diphenylphosphine adds to the carbon atom in ] to give (phenyl-(phenylmethyl)phosphoryl)benzene. |
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The preparation of phosphine ]s, ], and ]s are commonly accomplished by alkylating diphenylphosphine. The hydrogen atom connected to phosphorus undergoes Michael-like addition to activated alkenes, providing products with which to produce phosphine ligands such as ] (Ph<sub>2</sub>PC<sub>2</sub>H<sub>4</sub>PPh<sub>2</sub>) and ].<ref>{{OrgSynth |last=Cai |first=Dongwei |author2=J. F. Payack |author3=D. R. Bender |author4=D. L. Hughes |author5=T. R. Verhoeven |author6=P. J. Reider |year=1999 |title=(''R'')-(+)- and (''S'')-(−)-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP)|volume=76 |pages=6|prep=v76p0006}}</ref> via its bis] derivatives. Both the (''R'')- and (''S'')-]s, as well as the racemate, are commercially available. One of the wide applications include chemoselective hydrogenation, where BINAP is conjugated to rhodium. |
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:Ph<sub>2</sub>PH + PhCHO → Ph<sub>2</sub>P(O)CH<sub>2</sub>Ph |
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Diphenylphosphine and especially diphenylphosphide derivatives are nucleophiles, so they add to carbon – heteroatom double bonds.<ref name = piotrowski/> For example, in the presence of concentrated hydrochloric acid at 100 °C, diphenylphosphine adds to the carbon atom in ] to give (phenyl-(phenylmethyl)phosphoryl)benzene. |
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:Ph<sub>2</sub>PH + PhCHO → Ph<sub>2</sub>P(O)CH<sub>2</sub>Ph |
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Compared to tertiary phosphines, diphenylphosphine is weakly basic. The pKa of the protonated derivative is 0.03:<ref>C. A. Streuli, "Determination of Basicity of Substituted Phosphines by Nonaqueous Titrimetry", Analytical Chemistry 1960, volume 32, pages 985-987.{{doi|10.1021/ac60164a027}}</ref> |
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:Ph<sub>2</sub>PH<sub>2</sub><sup>+</sup> {{eqm}} Ph<sub>2</sub>PH + H<sup>+</sup> |
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===Handling properties=== |
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===Handling properties=== |
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During the handling of diphenylphosphine, care must be taken to avoid oxidation of diphenylphosphine.<ref name = Svara> Svara, J., Weferling, N., Hofmann, T. “Organic Phosphorus Compounds” Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons: New York, 2006. {{DOI|10.1002/14356007.a19_545.pub2}}.</ref> |
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Diphenylphosphine readily oxidizes.<ref name = Svara>{{Ullmann | author = Svara, J. | author2 = Weferling, N. | author3 = Hofmann, T. | title = Phosphorus Compounds, Organic | doi = 10.1002/14356007.a19_545.pub2}}</ref> |
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:Ph<sub>2</sub>PH + O<sub>2</sub> → Ph<sub>2</sub>P(O)OH |
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:Ph<sub>2</sub>PH + O<sub>2</sub> → Ph<sub>2</sub>P(O)OH |
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The use of the diphenylphosphine–borane complex, Ph<sub>2</sub>PH•BH<sub>3</sub> avoids the problem of phosphine oxidation by protecting the phosphine from oxidation and is available through chemical vendors.<ref name = piotrowski/> |
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An intermediate in this oxidation is ]. The use of the diphenylphosphine–borane complex, Ph<sub>2</sub>PH•BH<sub>3</sub> avoids the problem of phosphine oxidation by protecting the phosphine from oxidation and is available through chemical vendors.<ref name = piotrowski/> |
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==References== |
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==References== |
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{{Reflist}} |
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