Triphenyl phosphite

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

Triphenyl phosphite
Names
Preferred IUPAC name
Triphenyl phosphite
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.002.645
UNII
  • 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/h1-15H checkY
    Key: HVLLSGMXQDNUAL-UHFFFAOYSA-N checkY
  • 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/h1-15H
    Key: HVLLSGMXQDNUAL-UHFFFAOYAF
  • O(P(Oc1ccccc1)Oc2ccccc2)c3ccccc3
Properties
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)
low
Solubility organic solvents
-183.7·10−6 cm3/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 [77 °F], 100 kPa).
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Infobox references

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 P3+ that is less electrophilic than phosphorus trichloride:[1]

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

Triphenylphosphite is quaternized by methyl iodide:[2]

(C6H5O)3P + CH3I → [CH3(C6H5O)3P]+I−

Coordination complexes

Triphenylphosphite is a common ligand in coordination chemistry. It forms zero-valent complexes of the type M[P(OC6H5)3]4 (M = Ni, Pd, Pt). The nickel complex can be prepared by displacement of the diene from bis(cyclooctadiene)nickel:[3]

Ni(COD)2 + 4 P(OC6H5)3 → Ni[P(OC6H5)3]4 + 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 H2Fe[P(OC6H5)3]4.[4]

Polyamorphism

Triphenylphosphite is a notable example of polyamorphism in organic compounds, namely it exists in two different amorphous forms at temperatures about 200 K.[5] One polymorphic modification of triphenyl phosphite was obtained by means of crystallization in ionic liquids.[6]

References
  1. Leutkens, Jr., M. L.; Sattelberger, A. P.; Murray, H. H.; Basil, J. D.; Fackler, Jr. J. P. (1990). "Trimethylphosphine". Inorganic Syntheses. 28: 305–310. doi:10.1002/9780470132593.ch76. ISBN 9780470132593.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  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. Inorganic Syntheses. Vol. XVII. pp. 117–124. doi:10.1002/9780470132487.ch34. ISBN 9780470132487.
  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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