Triphenylphosphine

Summary

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

Triphenylphosphine
Skeletal structure
Ball-and-stick model of the triphenylphosphine molecule
Space-filling structure of PPh3
Names
Preferred IUPAC name
Triphenylphosphane[1]
Identifiers
  • 603-35-0 checkY
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:183318
ChemSpider
  • 11283 checkY
ECHA InfoCard 100.009.124 Edit this at Wikidata
EC Number
  • 210-036-0
  • 11776
RTECS number
  • SZ3500000
UNII
  • 26D26OA393 checkY
UN number 3077
  • DTXSID5026251 Edit this at Wikidata
  • InChI=1S/C18H15P/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18/h1-15H checkY
    Key: RIOQSEWOXXDEQQ-UHFFFAOYSA-N checkY
  • InChI=1/C18H15P/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18/h1-15H
    Key: RIOQSEWOXXDEQQ-UHFFFAOYAH
  • c1ccccc1P(c2ccccc2)c3ccccc3
Properties
C18H15P
Molar mass 262.292 g·mol−1
Appearance White Solid
Density 1.1 g cm−3, solid
Melting point 80 °C (176 °F; 353 K)
Boiling point 377 °C (711 °F; 650 K)
Insoluble
Solubility organic solvents
Acidity (pKa) 7.64[2] (pKa of conjugate acid in acetonitrile)

2.73[3] (pKa of conjugate acid, aqueous scale)

-166.8·10−6 cm3/mol
1.59; εr, etc.
Structure
Pyramidal
1.4 - 1.44 D [4]
Hazards
GHS labelling:
GHS07: Exclamation markGHS08: Health hazard
Danger
H302, H317, H350, H412
P201, P202, P261, P264, P270, P272, P273, P280, P281, P301+P312, P302+P352, P308+P313, P321, P330, P333+P313, P363, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
2
1
2
Flash point 180 °C (356 °F; 453 K)
Safety data sheet (SDS) Fisher Scientific
Related compounds
Trimethylphosphine
Phosphine
Related compounds
Triphenylamine
Triphenylarsine
Triphenylstibine
Triphenylphosphine oxide
Triphenylphosphine sulfide
Triphenylphosphine dichloride
Triphenylphosphine selenide
Pd(PPh3)4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Preparation and structure edit

Triphenylphosphine can be prepared in the laboratory by treatment of phosphorus trichloride with phenylmagnesium bromide or phenyllithium. The industrial synthesis involves the reaction between phosphorus trichloride, chlorobenzene, and sodium:[5]

PCl3 + 3 PhCl + 6 Na → PPh3 + 6 NaCl

Triphenylphosphine crystallizes in triclinic[6] and monoclinic modification.[7] In both cases, the molecule adopts a pyramidal structure with propeller-like arrangement of the three phenyl groups.

Principal reactions with chalcogens, halogens, and acids edit

Oxidation edit

Triphenylphosphine undergoes slow oxidation by air to give triphenylphosphine oxide, Ph3PO:

2 PPh3 + O2 → 2 OPPh3

This impurity can be removed by recrystallisation of PPh3 from either hot ethanol or isopropanol.[8] This method capitalizes on the fact that OPPh3 is more polar and hence more soluble in polar solvents than PPh3.

Triphenylphosphine abstracts sulfur from polysulfide compounds, episulfides, and elemental sulfur. Simple organosulfur compounds such as thiols and thioethers are unreactive, however. The phosphorus-containing product is triphenylphosphine sulfide, Ph3PS. This reaction can be employed to assay the "labile" S0 content of a sample, say vulcanized rubber. Triphenylphosphine selenide, Ph3PSe, may be easily prepared via treatment of PPh3 with red (alpha-monoclinic) Se. Salts of selenocyanate, SeCN, are used as the Se0 source. PPh3 can also form an adduct with Te, although this adduct primarily exists as (Ph3P)2Te rather than PPh3Te.[9]

Aryl azides react with PPh3 to give phosphanimines, analogues of OPPh3, via the Staudinger reaction. Illustrative is the preparation of triphenylphosphine phenylimide:

PPh3 + PhN3 → PhNPPh3 + N2

The phosphanimine can be hydrolyzed to the amine. Typically the intermediate phosphanimine is not isolated.

PPh3 + RN3 + H2O → OPPh3 + N2 + RNH2

Chlorination edit

Cl2 adds to PPh3 to give triphenylphosphine dichloride ([PPh3Cl]Cl), which exists as the moisture-sensitive phosphonium halide. This reagent is used to convert alcohols to alkyl chlorides in organic synthesis. Bis(triphenylphosphine)iminium chloride (PPN+Cl, formula [(C6H5)3P)2N]Cl is prepared from triphenylphosphine dichloride:[10]

2 Ph3PCl2 + NH2OH·HCl + Ph3P → {[Ph3P]2N}Cl + 4HCl + Ph3PO

Protonation edit

PPh3 is a weak base (aqueous pKaH = 2.73, determined electrochemically), although it is a considerably stronger base than NPh3 (estimated aqueous pKaH < –3).[11] It forms isolable triphenylphosphonium salts with strong acids such as HBr:[12]

P(C6H5)3 + HBr → [HP(C6H5)3]+Br

Organic reactions edit

PPh3 is widely used in organic synthesis. The properties that guide its usage are its nucleophilicity and its reducing character.[13] The nucleophilicity of PPh3 is indicated by its reactivity toward electrophilic alkenes, such as Michael-acceptors, and alkyl halides. It is also used in the synthesis of biaryl compounds, such as the Suzuki reaction.

Quaternization edit

PPh3 combines with alkyl halides to give phosphonium salts. This quaternization reaction is particularly fast for benzylic and allylic halides:

PPh3 + CH3I → [CH3PPh3]+I

These salts, which can often be isolated as crystalline solids, react with strong bases to form ylides, which are reagents in the Wittig reactions.

Aryl halides will quaternize PPh3 to give tetraphenylphosphonium salts:

PPh3 + PhBr → [PPh4]Br

The reaction however requires elevated temperatures and metal catalysts.

Mitsunobu reaction edit

In the Mitsunobu reaction, a mixture of triphenylphosphine and diisopropyl azodicarboxylate ("DIAD", or its diethyl analogue, DEAD) converts an alcohol and a carboxylic acid to an ester. DIAD is reduced as it serves as the hydrogen acceptor, and the PPh3 is oxidized to OPPh3.

Appel reaction edit

In the Appel reaction, a mixture of PPh3 and CX4 (X = Cl, Br) is used to convert alcohols to alkyl halides. Triphenylphosphine oxide (OPPh3) is a byproduct.

PPh3 + CBr4 + RCH2OH → OPPh3 + RCH2Br + HCBr3

This reaction commences with nucleophilic attack of PPh3 on CBr4, an extension of the quaternization reaction listed above.

Deoxygenation edit

The easy oxygenation of PPh3 is exploited in its use to deoxygenate organic peroxides, which generally occurs with retention of configuration:

PPh3 + RO2H → OPPh3 + ROH (R = alkyl)

It is also used for the decomposition of organic ozonides to ketones and aldehydes, although dimethyl sulfide is more popular for the reaction as the side product, dimethyl sulfoxide is more readily separated from the reaction mixture than triphenylphosphine oxide. Aromatic N-oxides are reduced to the corresponding amine in high yield at room temperature with irradiation:[14]

 

Sulfonation edit

Sulfonation of PPh3 gives tris(3-sulfophenyl)phosphine, P(C6H4-3-SO3)3 (TPPTS), usually isolated as the trisodium salt. In contrast to PPh3, TPPTS is water-soluble, as are its metal derivatives. Rhodium complexes of TPPTS are used in certain industrial hydroformylation reactions.[15]

 
3,3,3″-Phosphanetriyltris(benzenesulfonic acid) trisodium salt is a water-soluble derivative of triphenylphosphine.

Reduction to diphenylphosphide edit

Lithium in THF as well as Na or K react with PPh3 to give Ph2PM (M = Li, Na, K). These salts are versatile precursors to tertiary phosphines.[16][17] For example, 1,2-dibromoethane and Ph2PM react to give Ph2PCH2CH2PPh2. Weak acids such ammonium chloride, convert Ph2PM (M = Li, Na, K) into diphenylphosphine:[17]

(C6H5)2PM + H2O → (C6H5)2PH + MOH

Transition metal complexes edit

Triphenylphosphine binds well to most transition metals, especially those in the middle and late transition metals of groups 7–10.[18] In terms of steric bulk, PPh3 has a Tolman cone angle of 145°,[19] which is intermediate between those of P(C6H11)3 (170°) and P(CH3)3 (115°). In an early application in homogeneous catalysis, NiBr2(PPh3)2 was used by Walter Reppe for the synthesis of acrylate esters from alkynes, carbon monoxide, and alcohols.[20] The use of PPh3 was popularized by its use in the hydroformylation catalyst RhH(PPh3)3(CO).

Polymer-anchored PPh3 derivatives edit

Polymeric analogues of PPh3 are known whereby polystyrene is modified with PPh2 groups at the para position. Such polymers can be employed in many of the applications used for PPh3 with the advantage that the polymer, being insoluble, can be separated from products by simple filtration of reaction slurries. Such polymers are prepared via treatment of 4-lithiophenyl-substituted polystyrene with chlorodiphenylphosphine (PPh2Cl).

See also edit

References edit

  1. ^ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 431. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
  2. ^ Haav, Kristjan; Saame, Jaan; Kütt, Agnes; Leito, Ivo (2012). "Basicity of Phosphanes and Diphosphanes in Acetonitrile". European Journal of Organic Chemistry. 2012 (11): 2167–2172. doi:10.1002/ejoc.201200009. ISSN 1434-193X.
  3. ^ Allman, Tim; Goel, Ram G. (1982). "The Basicity of Phosphines". Canadian Journal of Chemistry. 60 (6): 716–722. doi:10.1139/v82-106.
  4. ^ Warchol, M.; Dicarlo, E. N.; Maryanoff, C. A.; Mislow, K. (1975). "Evidence for the Contribution of the Lone Pair to the Molecular Dipole Moment of Triarylphosphines". Tetrahedron Letters. 16 (11): 917–920. doi:10.1016/S0040-4039(00)72019-3.
  5. ^ Corbridge, D. E. C. (1995). Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. ISBN 0-444-89307-5.
  6. ^ Kooijman, H.; Spek, A. L.; van Bommel, K. J. C.; Verboom, W.; Reinhoudt, D. N. (1998). "A Triclinic Modification of Triphenylphosphine" (PDF). Acta Crystallographica. C54 (11): 1695–1698. doi:10.1107/S0108270198009305.
  7. ^ Dunne, B. J.; Orpen, A. G. (1991). "Triphenylphosphine: a Redetermination" (PDF). Acta Crystallographica. C47 (2): 345–347. doi:10.1107/S010827019000508X.
  8. ^ Armarego, W. L. F.; Perrin, D. D.; Perrin, D. R. (1980). Purification of Laboratory Chemicals (2nd ed.). New York: Pergamon. p. 455. ISBN 978-0-08-022961-4.
  9. ^ Jones, C. H. W.; Sharma, R. D. (1987). "125Te NMR and Mössbauer Spectroscopy of Tellurium-Phosphine Complexes and the Tellurocyanates". Organometallics. 6 (7): 1419–1423. doi:10.1021/om00150a009.
  10. ^ Ruff, J.K.; Schlientz, W.J. (1974). "μ‐Nitridobis(triphenylphosphorus)(l+) ("PPN") Salts with Metal Carbonyl Anions". Inorganic Syntheses. Vol. 15. pp. 84–90. doi:10.1002/9780470132463.ch19. ISBN 978-0-470-13246-3. {{cite book}}: |journal= ignored (help)
  11. ^ Allman, Tim; Goel, Ram G. (1982-03-15). "The basicity of phosphines". Canadian Journal of Chemistry. 60 (6): 716–722. doi:10.1139/v82-106. ISSN 0008-4042.
  12. ^ Hercouet, A.; LeCorre, M. (1988) Triphenylphosphonium bromide: A convenient and quantitative source of gaseous hydrogen bromide. Synthesis, 157–158
  13. ^ Cobb, J. E.; Cribbs, C. M.; Henke, B. R.; Uehling, D. E.; Hernan, A. G.; Martin, C.; Rayner, C. M. (2004). "Triphenylphosphine". In L. Paquette (ed.). Encyclopedia of Reagents for Organic Synthesis. New York: J. Wiley & Sons. doi:10.1002/047084289X.rt366.pub2. ISBN 0-471-93623-5.
  14. ^ Burke, S. D.; Danheiser, R. L. (1999). "Triphenylphosphine". Handbook of Reagents for Organic Synthesis, Oxidizing and Reducing Agents. Wiley. p. 495. ISBN 978-0-471-97926-5.
  15. ^ Herrmann, W. A.; Kohlpaintner, C. W. (2007). "Syntheses of Water‐Soluble Phosphines and their Transition Metal Complexes". Inorganic Syntheses. Vol. 32. pp. 8–25. doi:10.1002/9780470132630.ch2. ISBN 978-0-470-13263-0. {{cite book}}: |journal= ignored (help)
  16. ^ George W. Luther III; Gordon Beyerle (1977). "Lithium Diphenylphosphide and Diphenyl(Trimethylsilyl)Phosphine". Inorganic Syntheses. Vol. 17. pp. 186–188. doi:10.1002/9780470132487.ch51. ISBN 978-0-470-13248-7.
  17. ^ a b V. D. Bianco S. Doronzo (1976). "Diphenylphosphine". Inorganic Syntheses. Vol. 16. pp. 161–188. doi:10.1002/9780470132470.ch43. ISBN 978-0-470-13247-0.
  18. ^ Elschenbroich, C.; Salzer, A. (1992). Organometallics: A Concise Introduction (2nd ed.). Weinheim: Wiley-VCH. ISBN 3-527-28165-7.
  19. ^ Immirzi, A.; Musco, A. (1977). "A method to measure the size of phosphorus ligands in coordination complexes". Inorganica Chimica Acta. 25: L41–L42. doi:10.1016/S0020-1693(00)95635-4.
  20. ^ *Reppe, W.; Schweckendiek, W. J. (1948). "Cyclisierende Polymerisation von Acetylen. III Benzol, Benzolderivate und hydroaromatische Verbindungen". Justus Liebigs Annalen der Chemie. 560 (1): 104–116. doi:10.1002/jlac.19485600104.

External links edit

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