Misplaced Pages

Triphenyl phosphite: Difference between revisions

Article snapshot taken from Wikipedia with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.
Browse history interactively← Previous editContent deleted Content addedVisualWikitext
Revision as of 03:50, 27 December 2011 editShalalawudi (talk | contribs)2 editsNo edit summary← Previous edit Latest revision as of 02:29, 19 June 2024 edit undoVycl1994 (talk | contribs)Autopatrolled, Extended confirmed users126,018 editsNo edit summary 
(41 intermediate revisions by 27 users not shown)
Line 1: Line 1:
{{chembox {{chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 407450386
| Watchedfields = changed
⚫ | verifiedrevid = 470616535
| ImageFile_Ref = {{chemboximage|correct|??}} | ImageFile_Ref = {{chemboximage|correct|??}}
| ImageFile = P(OPh)3.png | ImageFile = P(OPh)3.png
| ImageFile1 = Triphenyl-phosphite-from-xtal-3D-bs-17.png
| ImageSize = 200px
| ImageFile1 = TriphenylPhosphite_3D_BallStick.png
| ImageSize1 = 250px | ImageSize1 = 250px
| IUPACName = Triphenyl phosphite | PIN = Triphenyl phosphite
⚫ |Section1={{Chembox Identifiers
| OtherNames =
⚫ | Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 7259 | ChemSpiderID = 7259
Line 18: Line 18:
| StdInChIKey = HVLLSGMXQDNUAL-UHFFFAOYSA-N | StdInChIKey = HVLLSGMXQDNUAL-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 101-02-0 | CASNo = 101-02-0
| UNII_Ref = {{fdacite|changed|FDA}}
| UNII = 9P45GRD24X
| PubChem = 7540 | PubChem = 7540
| SMILES = O(P(Oc1ccccc1)Oc2ccccc2)c3ccccc3 | SMILES = O(P(Oc1ccccc1)Oc2ccccc2)c3ccccc3
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = C<sub>18</sub>H<sub>15</sub>O<sub>3</sub>P | Formula = C<sub>18</sub>H<sub>15</sub>O<sub>3</sub>P
| MolarMass = 310.28 g/mol | MolarMass = 310.28 g/mol
| Appearance = colourless liquid | Appearance = colourless liquid
| Density = 1.184 g/mL | Density = 1.184 g/mL
| MeltingPt = 22–24 °C | MeltingPtC = 22 to 24
| BoilingPt = 360 °C | BoilingPtC = 360
| Solubility = organic solvents | Solubility = low
| SolubleOther = organic solvents
| MagSus = -183.7·10<sup>−6</sup> cm<sup>3</sup>/mol
}} }}
| Section3 = {{Chembox Hazards |Section3={{Chembox Hazards
| MainHazards = flammable | MainHazards = flammable
| FlashPt =
| Autoignition =
}} }}
}} }}
'''Triphenyl phosphite''' is the ] with the ] P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub>. It is a colourless viscous liquid.


==Preparation==
'''Triphenyl phosphite''' is the ] with the ] P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub>. This colourless viscous liquid is the ester of ] and ]. It is used as a ] in ]. Nickel complexes of this ligand are ]s for the ] of ]s.
⚫ Triphenylphosphite is prepared from ] and ] in the presence of a catalytic amount of base:
⚫ :PCl<sub>3</sub> + 3 HOC<sub>6</sub>H<sub>5</sub> → P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> + 3 HCl


==Reactions==
⚫ Triphenylphosphite is prepared from phosphorus trichloride and phenol in the presence of a base:
Triphenylphosphite is a precursor to ], it serves as a source of P<sup>3+</sup> that is less electrophilic than phosphorus trichloride:<ref>{{cite book | series = ] |author1=Leutkens, M. L. Jr. |author2=Sattelberger, A. P. |author3=Murray, H. H. |author4=Basil, J. D. |author5-link=John P. Fackler Jr. |author5=Fackler, J. P. Jr. |chapter=Trimethylphosphine | year = 1990 | title = Inorganic Syntheses | volume = 28 | pages = 305–310 | doi = 10.1002/9780470132593.ch76|isbn=978-0-470-13259-3 }}</ref>
⚫ :PCl<sub>3</sub> + 3 HOC<sub>6</sub>H<sub>5</sub> → P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> + 3 HCl
: (C<sub>6</sub>H<sub>5</sub>O)<sub>3</sub>P + 3{{nbsp}}CH<sub>3</sub>MgBr → P(CH<sub>3</sub>)<sub>3</sub> + 3{{nbsp}}"MgBrOC<sub>6</sub>H<sub>5</sub>"


Triphenylphosphite is quaternized by ]:<ref>{{cite journal |author=H. N. Rydon|doi=10.15227/orgsyn.051.0044|title=Alkyl Iodides: Neopentyl Iodide and Iodocyclohexane|journal=Organic Syntheses|year=1971|volume=51|page=44}}</ref>
] is prepared from triphenylphosphite:<ref>Leutkens, Jr., M. L.; Sattelberger, A. P.; Murray, H. H.; Basil, J. D.; Fackler, Jr., J. P. "Trimethylphosphine" Inorganic Syntheses, 1990, volume 28, pages 305-310. ISBN 0-471-52619-3</ref>
: 3 CH<sub>3</sub>MgBr + P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → P(CH<sub>3</sub>)<sub>3</sub> + 3 MgBrOC<sub>6</sub>H<sub>5</sub> : (C<sub>6</sub>H<sub>5</sub>O)<sub>3</sub>P + CH<sub>3</sub>I → <sup>+</sup>I<sup>−</sup>


===Coordination complexes===
⚫ Triphenylphosphite is a notable example of ] in organic compounds, namely it exists in two different amorphous forms at temperatures about 200 K.<ref>{{cite journal|doi=10.1021/jp9530820|title=Supercooled Liquids and Polyamorphism†|year=1996|last1=Ha|first1=Alice|last2=Cohen|first2=Itai|last3=Zhao|first3=Xiaolin|last4=Lee|first4=Michelle|last5=Kivelson|first5=Daniel|journal=The Journal of Physical Chemistry|volume=100|pages=1}}</ref>
⚫ Triphenylphosphite is a common ] in ]. It forms zero-valent complexes of the type M<sub>4</sub> (M = Ni, Pd, Pt). The nickel complex can be prepared by displacement of the diene from ]:<ref>{{cite book|doi=10.1002/9780470132487.ch34|chapter=Olefin, Acetylene, Phosphine, Isocyanide, and Diazene Complexes of Nickel(0)|year=1977|last1=Ittel|first1=Steven D.|title=Inorganic Syntheses|pages=117–124|volume=XVII|isbn=978-0-470-13248-7}}</ref>

==Representative coordination complexes==
⚫ Triphenylphosphite forms zero-valent complexes of the type M<sub>4</sub> for M = Ni, Pd, Pt. The colourless nickel complex (melting point&nbsp;147 °C) can be prepared from the nickel(0) complex of ]:<ref>Ittel, S. D. "Olefin, Acetylene, Phosphine, Isocyanide, and Diazene Complexes of Nickel(0)" Inorganic Syntheses, 1977, volume XVII, p. 117–124. ISBN 0-07-044327-0,</ref>
: Ni(COD)<sub>2</sub> + 4 P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → Ni<sub>4</sub> + 2 COD : Ni(COD)<sub>2</sub> + 4 P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → Ni<sub>4</sub> + 2 COD
⚫ Related complexes are ]s for the ] of ]s. It also forms a variety of Fe(0) and Fe(II) complexes such as the di] H<sub>2</sub>Fe<sub>4</sub>.<ref>{{cite journal|doi=10.1021/ja00768a022|title=Stereochemically Nonrigid Six-Coordinate Molecules. II. Preparations and Reactions of Tetrakis(organophosphorus)metal Dihydride Complexes|year=1972|last1=Gerlach|first1=D. H.|last2=Peet|first2=W. G.|last3=Muetterties|first3=E. L.|journal=Journal of the American Chemical Society|volume=94|pages=4545|issue=13}}</ref>


==Polyamorphism==
⚫ It also forms a variety of Fe(O) and Fe(II) complexes such as the di] H<sub>2</sub>Fe<sub>4</sub>.<ref>{{cite journal|doi=10.1021/ja00768a022|title=Stereochemically nonrigid six-coordinate molecules. II. Preparations and reactions of tetrakis(organophosphorus)metal dihydride complexes|year=1972|last1=Gerlach|first1=D. H.|last2=Peet|first2=W. G.|last3=Muetterties|first3=E. L.|journal=Journal of the American Chemical Society|volume=94|pages=4545|issue=13}}</ref><ref></ref>
⚫ Triphenylphosphite is a notable example of ] in organic compounds, namely it exists in two different amorphous forms at temperatures about 200 K.<ref>{{cite journal|doi=10.1021/jp9530820|title=Supercooled Liquids and Polyamorphism†|year=1996|last1=Ha|first1=Alice|last2=Cohen|first2=Itai|last3=Zhao|first3=Xiaolin|last4=Lee|first4=Michelle|last5=Kivelson|first5=Daniel|journal=The Journal of Physical Chemistry|volume=100|pages=1–4}}</ref> One polymorphic modification of triphenyl phosphite was obtained by means of crystallization in ]s.<ref>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. </ref>


==References== ==References==
{{reflist}} {{reflist}}


⚫ ]
] ]
⚫ ]

]
]

Latest revision as of 02:29, 19 June 2024

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
Categories: