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|Verifiedfields = changed |
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| verifiedrevid = 289925773 |
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|Watchedfields = changed |
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| Name = Trimethylphosphine |
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|verifiedrevid = 407272775 |
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| ImageFile = PMe3.png |
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|ImageFile = Trimethylphosphine Structural Formula.svg |
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|ImageFile_Ref = {{chemboximage|correct|??}} |
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| ImageName = trimethylphosphine |
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|ImageSize = 200 |
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| ImageFile1 = Trimethylphosphine-A-3D-balls.png |
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|ImageName = Stereo, skeletal formula of trimethylphosphine with the lone pair of electrons shown, and all explicit hydrogens added |
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|ImageFile1 = Trimethylphosphine-A-3D-balls.png |
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| ImageName1 = Ball-and-stick model of trimethylphosphine |
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|ImageFile1_Ref = {{chemboximage|correct|??}} |
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| IUPACName = Trimethylphosphine |
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|ImageSize1 = 200 |
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| OtherNames = trimethylphosphane |
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|ImageName1 = Ball and stick model of trimethylphosphine |
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| Section1 = {{Chembox Identifiers |
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|ImageFile2 = Trimethylphosphine-3D-vdW.png |
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| CASNo_Ref = {{cascite}} |
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|ImageSize2 = 200 px |
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| CASNo = 594-09-2 |
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|PIN = Trimethylphosphane |
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| RTECS = |
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|SystematicName = Trimethylphosphane<ref name = "trimethylphosphine (CHEBI:35890)">{{Cite web|title = Trimethylphosphine (CHEBI:35890)|url = https://www.ebi.ac.uk/chebi/searchId.do?chebiId=35890|work = Chemical Entities of Biological Interest (ChEBI)|publisher = European Bioinformatics Institute|access-date = 25 September 2011|location = UK|date = 6 June 2006|at = IUPAC Names}}</ref> (substitutive)<br /> |
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Trimethylphosphorus<ref name = "trimethylphosphine (CHEBI:35890)" /> (additive) |
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| Section2 = {{Chembox Properties |
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|Section1={{Chembox Identifiers |
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| Formula = C<sub>3</sub>H<sub>9</sub>P |
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|CASNo = 594-09-2 |
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| MolarMass = 76.07 g/mol |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| Appearance = Colorless liquid, ] |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| Density = 0.735 g/cm<sup>3</sup> liquid |
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| UNII = 5FL6SQK9H3 |
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| Solubility = low |
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|PubChem = 68983 |
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| Solvent = other solvents |
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|ChemSpiderID = 62205 |
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| SolubleOther = most organic solvents |
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|ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| MeltingPt = -86 °C |
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|EINECS = 209-823-1 |
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| BoilingPt = 38-39 °C |
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|UNNumber = 1993 |
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|MeSHName = trimethyl+phosphine |
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| Section3 = {{Chembox Structure |
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|ChEBI = 35890 |
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| Coordination = Trigonal pyramidal |
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|ChEBI_Ref = {{ebicite|changed|EBI}} |
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| Dipole = 1.19 Debye |
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|Beilstein = 969138 |
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|SMILES = CP(C)C |
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| Section7 = {{Chembox Hazards |
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|StdInChI = 1S/C3H9P/c1-4(2)3/h1-3H3 |
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| MainHazards = toxic |
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|StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| FlashPt = |
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|StdInChIKey = YWWDBCBWQNCYNR-UHFFFAOYSA-N |
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| RPhrases = 11-36/37/38 |
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|StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| SPhrases = 9-16-26-36/37/39 |
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| Section8 = {{Chembox Related |
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|Section2={{Chembox Properties |
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|C=3 | H=9 | P=1 |
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| OtherCpds = ]<br />]<br />] |
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|Appearance = Colorless liquid |
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|Density = 735 mg cm<sup>−3</sup> |
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|MeltingPtC = -86 |
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|BoilingPtC = 38 to 39 |
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|VaporPressure = 49.9 kPa (at 20 °C) |
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|Section3={{Chembox Structure |
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|Coordination = Trigonal pyramidal |
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|Dipole = 1.19 Debye |
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|Section4={{Chembox Hazards |
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|GHSPictograms = {{GHS flame}} {{GHS exclamation mark}} |
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|GHSSignalWord = '''DANGER''' |
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|HPhrases = {{H-phrases|225|315|319|335}} |
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|PPhrases = {{P-phrases|210|261|305+351+338}} |
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|FlashPtC = -19 |
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|Section8={{Chembox Related |
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|OtherCompounds = ]<br />]<br />]<br />] |
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'''Trimethylphosphine''' is the ] with the formula P(CH<sub>3</sub>)<sub>3</sub>, commonly abbreviated PMe<sub>3</sub>. This colorless liquid has a strongly unpleasant odour, which is characteristic of alkylphosphines. It is a ] molecule with C<sub>3v</sub> ], similar to ] (NH<sub>3</sub>) and ] (PH<sub>3</sub>). As a ligand, its ] is 118°.<ref>G. L. Miessler and D. A. Tarr “Inorganic Chemistry” 3rd Ed, Pearson/Prentice Hall publisher, ISBN 0-13-035471-6.</ref> This angle, close to the optimal angles for sp<sup>2</sup>-hybridisation, is an indication for the hybridisation of the phosphorus atom. The lone pair is left in an almost straight p-], so it points rather localized outward, in contrast to the higher members of the ], to open the route to the rather ] properties of the compound. |
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'''Trimethylphosphine''' is an ] with the formula P(CH<sub>3</sub>)<sub>3</sub>, commonly abbreviated as PMe<sub>3</sub>. This colorless liquid has a strongly unpleasant odor, characteristic of alkylphosphines. The compound is a common ] in ]. |
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==Structure and bonding== |
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PMe<sub>3</sub> is prepared using ]s:<ref>{{cite journal | editor = Robert J. Angelici | journal = ] | author = Leutkens, Jr., M. L.; Sattelberger, A. P.; Murray, H. H.; Basil, J. D.; Fackler, Jr., J. P. | year = 1990 | title = Trimethylphosphine | volume = 28 | pages = 305–310 | isbn = 0-471-52619-3 | doi = 10.1002/9780470132593.ch76 | publisher = J. Wiley & Sons | location = New York}}</ref> |
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It is a ] molecule with approximate ''C''<sub>3''v''</sub> ]. The C–P–C bond angles are approximately 98.6°.<ref name=Schmidbaur/> |
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: 3 ] + ] → P(CH<sub>3</sub>)<sub>3</sub> + 3 C<sub>6</sub>H<sub>5</sub>OMgBr |
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The synthesis is conducted in a dibutyl ether, from which the more volatile PMe<sub>3</sub> can be distilled. |
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The C–P–C bond angles are consistent with the notion that phosphorus predominantly uses the 3p orbitals for forming bonds and that there is little sp hybridization of the phosphorus atom. The latter is a common feature of the chemistry of phosphorus. As a result, the lone pair of trimethylphosphine has predominantly s-character as is the case for phosphine, PH<sub>3</sub>.<ref>E. Fluck, The Chemistry of Phosphine, Topics in Current Chemistry Vol. 35, 64 pp, 1973.</ref> |
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==Coordination chemistry== |
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Trimethylphosphine is a highly basic ] that forms complexes with most metals. The synthesis of an illustrative example is shown: |
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PMe<sub>3</sub> can be prepared by the treatment of ] with ]:<ref>{{cite book | series = ] |author1=Leutkens Jr., M. L. |author2=Sattelberger, A. P. |author3=Murray, H. H. |author4=Basil, J. D. |author5=Fackler J. P. Jr. |author5-link=John P. Fackler 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> |
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:PMe<sub>3</sub> + ] → Fe(CO)<sub>4</sub>PMe<sub>3</sub> + CO |
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Its complex with silver iodide, AgI(PMe<sub>3</sub>) is a weighable, air stable solid that releases PMe<sub>3</sub> upon heating. |
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: 3 CH<sub>3</sub>MgCl + P(OC<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → P(CH<sub>3</sub>)<sub>3</sub> + 3 C<sub>6</sub>H<sub>5</sub>OMgCl |
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The synthesis is conducted in ], from which the more volatile PMe<sub>3</sub> can be distilled. |
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==Reactions== |
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X (X = Br, I)|journal=Chemical Communications |year=2011|volume=47|issue = 48|pages=12828–12830|doi=10.1039/C1CC15457E|pmid = 22048609}}</ref>]] |
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With a pK<sub>a</sub> of 8.65, PMe<sub>3</sub> reacts with strong acids to give salts X.<ref name=Schmidbaur>{{cite book|doi=10.1002/0470862106.ia177|chapter=P-Donor Ligands|editor=Charles A. McAuliffe, Anthony G. Mackie|title=Encyclopedia of Inorganic Chemistry, First Edition |year=2006 |last1=Schier |first1=Annette |last2=Schmidbaur |first2=Hubert |isbn=0-470-86078-2 }}</ref> This reaction is reversible. With strong bases, such as ]s, a methyl group undergoes deprotonation to give PMe<sub>2</sub>CH<sub>2</sub>Li. |
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PMe<sub>3</sub> is easily oxidised to the phosphine oxide with oxygen. It reacts with ] to give ].<ref>{{cite book|chapter=Trimethylphosphonium Methylide (Trimethyl Methylenephosphorane)|author=H. F. Klein|title=Inorganic Syntheses|year=1978|volume=XVIII|pages=138–140|doi=10.1002/9780470132494.ch23|isbn=978-0-470-13249-4}}</ref> |
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===Coordination chemistry=== |
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Trimethylphosphine is a highly basic ] that forms complexes with most metals. As a ligand, trimethylphosphine's ] is 118°.<ref>G. L. Miessler and D. A. Tarr ''Inorganic Chemistry'', 3rd Ed, Pearson/Prentice Hall publisher, {{ISBN|0-13-035471-6}}.</ref> This angle is an indication of the amount of steric protection that this ligand provides to the metal that to which it is bound. |
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Being a relatively compact phosphine, several can bind to a single transition metal, as illustrated by the existence of Pt(PEt<sub>3</sub>)<sub>4</sub>.<ref>{{cite book|chapter=Tetrakis(Triethylphosphine)Platinum(0)|author=T. Yoshida |author2=T. Matsuda |author3=S. Otsuka |title=Inorganic Syntheses |volume=28|year=1990|pages=122–123|doi=10.1002/9780470132593.ch32 |isbn=978-0-470-13259-3 }}</ref> Its complex with silver iodide, AgI(PMe<sub>3</sub>) is an air-stable solid that releases PMe<sub>3</sub> upon heating. |
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==Safety== |
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==Safety== |
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PMe<sub>3</sub> is toxic and ]. It converts to a much safer ] upon treatment with ] or ].<ref>{{cite web | website=sigmaaldrich.com|title=Trimethylphosphine solution | url=http://www.sigmaaldrich.com/catalog/product/aldrich/324116?lang=en®ion=US&cm_sp=Insite-_-prodRecCold_xorders-_-prodRecCold2-2 | access-date=1 August 2023}}</ref> |
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PMe<sub>3</sub> is potentially ] as well as toxic. PMe<sub>3</sub> can be converted to non-pyrophoric ] by treatment with dilute ]. |
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==References== |
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==References== |
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