Triphenyl phosphite

Triphenyl phosphite
Names
	Preferred IUPAC name Triphenyl phosphite
Identifiers
CAS Number	101-02-0 ;
3D model (JSmol)	Interactive image;
ChemSpider	7259 ;
ECHA InfoCard	100.002.645
PubChem CID	7540;
UNII	9P45GRD24X ;
CompTox Dashboard (EPA)	DTXSID0026252 ;
	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/h1-15H Key: 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/h1-15H Key: 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)	-183.7·10−6 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). verify (what is ?) Infobox references

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 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

^ 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.
^ H. N. Rydon (1971). "Alkyl Iodides: Neopentyl Iodide and Iodocyclohexane". Organic Syntheses. 51: 44. doi:10.15227/orgsyn.051.0044.
^ 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.
^ 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.
^ 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.
^ 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

[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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