Triphenyl phosphite

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Triphenyl phosphite
P(OPh)3.png
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Names
Preferred IUPAC name
Triphenyl phosphite
Identifiers
3D model (JSmol)
ChemSpider
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PubChem CID
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 Yes check.svgY
    Key: HVLLSGMXQDNUAL-UHFFFAOYSA-N Yes check.svgY
  • 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
Appearancecolourless 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

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

Contents

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]

Related Research Articles

Nickel(II) chloride Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

The phosphonium cation describes polyatomic cations with the chemical formula PR+
4
. These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions.

Phosphorus trichloride Chemical compound

Phosphorus trichloride is a inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

Phosphorus trifluoride (formula PF3), is a colorless and odorless gas. It is highly toxic and reacts slowly with water. Its main use is as a ligand in metal complexes. As a ligand, it parallels carbon monoxide in metal carbonyls, and indeed its toxicity is due to its binding with the iron in blood hemoglobin in a similar way to carbon monoxide.

Phosphorous acid (or phosphonic acid (singular)) is the compound described by the formula H3PO3. This acid is diprotic (readily ionizes two protons), not triprotic as might be suggested by this formula. Phosphorous acid is an intermediate in the preparation of other phosphorus compounds. Organic derivatives of phosphorous acid, compounds with the formula RPO3H2, are called phosphonic acids.

Iron pentacarbonyl Chemical compound

Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5. Under standard conditions Fe(CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis.

Phosphite ester

In chemistry a phosphite ester or organophosphite usually refers to an organophosphorous compound with the formula P(OR)3. They can be considered as esters of an unobserved tautomer phosphorous acid, H3PO3, with the simplest example being trimethylphosphite, P(OCH3)3. Some phosphites can be considered esters of the dominant tautomer of phosphorous acid (HP(O)(OH)2). The simplest representative is dimethylphosphite with the formula HP(O)(OCH3)2. Both classes of phosphites are usually colorless liquids.

(Benzylideneacetone)iron tricarbonyl Chemical compound

(Benzylideneacetone)iron tricarbonyl is the organoiron compound with the formula (C6H5CH=CHC(O)CH3)Fe(CO)3. It is a reagent for transferring the Fe(CO)3 unit. This red-colored compound is commonly abbreviated (bda)Fe(CO)3.

Trimethylphosphine Chemical compound

Trimethylphosphine is a neutral organophosphorus compound with the formula P(CH3)3, commonly abbreviated as PMe3. This colorless liquid has a strongly unpleasant odor, characteristic of alkylphosphines. The compound is a common ligand in coordination chemistry.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

Thiophosphoryl chloride Chemical compound

Thiophosphoryl chloride is an inorganic compound with the formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

Triethyl phosphite Chemical compound

Triethyl phosphite is an organophosphorus compound with the formula P(OCH2CH3)3, often abbreviated P(OEt)3. It is a colorless, malodorous liquid. It is used as a ligand in organometallic chemistry and as a reagent in organic synthesis

Trimethyl phosphite Chemical compound

Trimethyl phosphite is an organophosphorus compound with the formula P(OCH3)3, often abbreviated P(OMe)3. It is a colorless liquid with a highly pungent odor. It is the simplest phosphite ester and finds used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three methoxy groups.

Chlorodiphenylphosphine Chemical compound

Chlorodiphenylphosphine is an organophosphorus compound with the formula (C6H5)2PCl, abbreviated Ph2PCl. It is a colourless oily liquid with a pungent odor that is often described as being garlic-like and detectable even in the ppb range. It is useful reagent for introducing the Ph2P group into molecules, which includes many ligands. Like other halophosphines, Ph2PCl is reactive with many nucleophiles such as water and easily oxidized even by air.

Bis(cyclooctadiene)nickel(0) Chemical compound

Bis(cyclooctadiene)nickel(0) is the organonickel compound with the formula Ni(C8H12)2, also written Ni(cod)2. It is a diamagnetic coordination complex featuring tetrahedral nickel(0) bound to the alkene groups in two 1,5-cyclooctadiene ligands. This highly air-sensitive yellow solid is a common source of Ni(0) in chemical synthesis.

Molybdenum(III) chloride Chemical compound

Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals.

Chlorobis(dppe)iron hydride Chemical compound

Chlorobis(dppe)iron hydride is a coordination complex with the formula HFeCl(dppe)2, where dppe is the bidentate ligand 1,2-bis(diphenylphosphino)ethane. It is a red-violet solid. The compound has attracted much attention as a precursor to dihydrogen complexes.

Diethylphosphite Chemical compound

Diethylphosphite is the organophosphorus compound with the formula (C2H5O)2P(O)H. It is a popular reagent for generating other organophosphorus compounds, exploiting the high reactivity of the P-H bond. Diethylphosphite is a colorless liquid. The molecule is tetrahedral.

Lithium diphenylphosphide Chemical compound

Lithium diphenylphosphide contains lithium and the organophosphorus anion with the formula (C6H5)2PLi. It is an air-sensitive solid that is used in the preparation of diphenylphosphino compounds. As an ether complex, the lithium salt is dark red.

Triethylphosphine is the organophosphorus compound with the formula P(CH2CH3)3, commonly abbreviated as PEt3. It is a colorless liquid with an unpleasant odor characteristic of alkylphosphines. The compound is a common ligand in organometallic chemistry, such as in auranofin.

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