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Triphenyl phosphite

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Triphenyl phosphite
Names
Preferred IUPAC name Triphenyl phosphite
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.002.645 Edit this at Wikidata
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C18H15O3P/c1-4-10-16(11-5-1)19-22(20-17-12-6-2-7-13-17)21-18-14-8-3-9-15-18/h1-15HKey: HVLLSGMXQDNUAL-UHFFFAOYSA-N
  • InChI=1/C18H15O3P/c1-4-10-16(11-5-1)19-22(20-17-12-6-2-7-13-17)21-18-14-8-3-9-15-18/h1-15HKey: HVLLSGMXQDNUAL-UHFFFAOYAF
SMILES
  • O(P(Oc1ccccc1)Oc2ccccc2)c3ccccc3
Properties
Chemical formula C18H15O3P
Molar mass 310.28 g/mol
Appearance colourless liquid
Density 1.184 g/mL
Melting point 22 to 24 °C (72 to 75 °F; 295 to 297 K)
Boiling point 360 °C (680 °F; 633 K)
Solubility in water low
Solubility organic solvents
Magnetic susceptibility (χ) -183.7·10 cm/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards flammable
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Triphenyl phosphite is the organophosphorus compound with the formula P(OC6H5)3. It is a colourless viscous liquid.

Preparation

Triphenylphosphite is prepared from phosphorus trichloride and phenol in the presence of a catalytic amount of base:

PCl3 + 3 HOC6H5 → P(OC6H5)3 + 3 HCl

Reactions

Triphenylphosphite is a precursor to trimethylphosphine, it serves as a source of P that is less electrophilic than phosphorus trichloride:

(C6H5O)3P + 3 CH3MgBr → P(CH3)3 + 3 "MgBrOC6H5"

Triphenylphosphite is quaternized by methyl iodide:

(C6H5O)3P + CH3I → I

Coordination complexes

Triphenylphosphite is a common ligand in coordination chemistry. It forms zero-valent complexes of the type M4 (M = Ni, Pd, Pt). The nickel complex can be prepared by displacement of the diene from bis(cyclooctadiene)nickel:

Ni(COD)2 + 4 P(OC6H5)3 → Ni4 + 2 COD

Related complexes are homogeneous catalysts for the hydrocyanation of alkenes. It also forms a variety of Fe(0) and Fe(II) complexes such as the dihydride H2Fe4.

Polyamorphism

Triphenylphosphite is a notable example of polyamorphism in organic compounds, namely it exists in two different amorphous forms at temperatures about 200 K. One polymorphic modification of triphenyl phosphite was obtained by means of crystallization in ionic liquids.

References

  1. Leutkens, M. L. Jr.; Sattelberger, A. P.; Murray, H. H.; Basil, J. D.; Fackler, J. P. Jr. (1990). "Trimethylphosphine". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 305–310. doi:10.1002/9780470132593.ch76. ISBN 978-0-470-13259-3.
  2. H. N. Rydon (1971). "Alkyl Iodides: Neopentyl Iodide and Iodocyclohexane". Organic Syntheses. 51: 44. doi:10.15227/orgsyn.051.0044.
  3. Ittel, Steven D. (1977). "Olefin, Acetylene, Phosphine, Isocyanide, and Diazene Complexes of Nickel(0)". Inorganic Syntheses. Vol. XVII. pp. 117–124. doi:10.1002/9780470132487.ch34. ISBN 978-0-470-13248-7.
  4. Gerlach, D. H.; Peet, W. G.; Muetterties, E. L. (1972). "Stereochemically Nonrigid Six-Coordinate Molecules. II. Preparations and Reactions of Tetrakis(organophosphorus)metal Dihydride Complexes". Journal of the American Chemical Society. 94 (13): 4545. doi:10.1021/ja00768a022.
  5. Ha, Alice; Cohen, Itai; Zhao, Xiaolin; Lee, Michelle; Kivelson, Daniel (1996). "Supercooled Liquids and Polyamorphism†". The Journal of Physical Chemistry. 100: 1–4. doi:10.1021/jp9530820.
  6. D.G. Golovanov, K.A. Lyssenko, M.Yu. Antipin, Ya.S. Vygodskii, E.I. Lozinskaya, A.S. Shaplov. ”Long-awaited polymorphic modification of triphenyl phosphite“, Cryst. Eng. Comm., 2005, v. 7, no. 77, P.465 – 468. doi: 10.1039/b505052a
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