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{{chembox | |||
| verifiedrevid = 451151193 | |||
| Name = Dimethylphenylphosphine | |||
| ImageFile = Dimethylphenylphosphine.png | |||
| ImageSize = | |||
| ImageName = Dimethylphenylphosphine | |||
| IUPACName = Dimethylphenylphosphane | |||
| OtherNames = Dimethylphenylphosphine | |||
| Section1 = {{Chembox Identifiers | |||
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | |||
| ChemSpiderID = 62800 | |||
| PubChem = 69597 | |||
| InChI = 1/C8H11P/c1-9(2)8-6-4-3-5-7-8/h3-7H,1-2H3 | |||
| ChEBI_Ref = {{ebicite|correct|EBI}} | |||
| ChEBI = 30671 | |||
| SMILES = P(c1ccccc1)(C)C | |||
| InChIKey = HASCQPSFPAKVEK-UHFFFAOYAS | |||
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} | |||
| StdInChI = 1S/C8H11P/c1-9(2)8-6-4-3-5-7-8/h3-7H,1-2H3 | |||
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | |||
| StdInChIKey = HASCQPSFPAKVEK-UHFFFAOYSA-N | |||
| CASNo_Ref = {{cascite|correct|CAS}} | |||
| CASNo = 672-66-2 | |||
| EINECS = 211-595-3 | |||
}} | |||
| Section2 = {{Chembox Properties | |||
| Formula = C<sub>8</sub>H<sub>11</sub>P | |||
| MolarMass = 138.14 g/mol | |||
| Appearance = Colorless light pale yellow liquid | |||
| Density = 0.971 g/cm<sup>3</sup> | |||
| Solubility = Insoluble | |||
| MeltingPt = N/A | |||
| BoilingPt = 74-75°C @ 12 mmHg | |||
}} | |||
| Section3 = {{Chembox Structure | |||
| MolShape = Pyramidal | |||
}} | |||
| Section7 = {{Chembox Hazards | |||
| ExternalMSDS = [http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do] | |||
| FlashPtC = 49 | |||
| RPhrases = {{R10}} {{R36}} {{R37}} {{R38}} | |||
| SPhrases = {{S26}} {{S36}} | |||
}} | |||
}} | |||
''' Dimethylphenylphosphine ''' is an [[organophosphorus compound]] with a formula P(C<sub>6</sub>H<sub>5</sub>)(CH<sub>3</sub>)<sub>2</sub>. The [[phosphorus]] is connected to a [[phenyl]] group and two [[methyl]] groups. This colorless air sensitive liquid is commonly used as a [[ligand]] in [[transition metal complex]]es. These complexes are often soluble in organic solvents. | |||
==Preparation== | |||
Dimethylphenylphosphine is prepared by the reaction of [[Grignard reaction|methylmagnesium halide]] with [[dichlorophenylphosphine]]. | |||
:(C<sub>6</sub>H<sub>5</sub>)Cl<sub>2</sub>P + 2CH<sub>3</sub>MgBr → (C<sub>6</sub>H<sub>5</sub>)(CH<sub>3</sub>)<sub>2</sub>P + 2MgBrCl | |||
The [[phosphine]] is purified by distillation under reduced pressure.<ref>C. Frajerman; B. Meunier; M. E. Strem., ''Inorganic Syntheses'', Preparation of Dimethylphenylphosphine, 2007, volume 22, 133-135, {{DOI|10.1002/9780470132531}}. ch29</ref> | |||
A solution of (C<sub>6</sub>H<sub>5</sub>)(CH<sub>3</sub>)<sub>2</sub>P in CDCl<sub>3</sub> shows [[proton NMR]] signals at δ = 7.0-7.5 and a doublet at δ = 1.2. The [[phosphorus-31 NMR]] spectrum shows a singlet at -45.89 ppm in CDCl<sub>3</sub>.<ref>Laszlo T. Mika, Laszlo Orha, Norbert Farkas and Istvan T. Horvath, Organometallics, 2009, 28, 1593</ref> | |||
==Structure and properties== | |||
Dimethylphenylphosphine is a [[Trigonal pyramidal molecular geometry|pyramidal molecule]] where the [[phenyl]] group and two [[methyl]] groups are connected to the phosphorus. The [[bond length]] and angles are the following: P-C<sub>Me</sub>: 1.844, P-C<sub>Ph</sub>: 1.845 Å, C-C: 1.401 Å, C-H<sub>Me</sub>: 1.090 Å, C-H<sub>Ph</sub>: 1.067 Å, C-P-C: 96.9°, C-P-C (ring): 103.4°, P-C-H: 115.2°.<ref>Novikov, V.P., Kolomeets, V.I., Syshchikov, Yu.N., Vilkov, L.V., Yarkov, A.V., Tsvetkov, E.N., Raevskii, O.A.: Zh. Strukt. Khim., ''J. Struc. Chem''., Investigation of structure of dimethylphenylphosphine by means of gas-phase electron diffraction and vibrational spectroscopy, 1984, volume 25, No.5, 688. {{DOI|10.1007/BF00747909}}</ref> | |||
==Comparisons with related phosphine ligands== | |||
The υ<sub>CO</sub> of Ir-Cl(CO)(PPh<sub>3</sub>)<sub>2</sub> and Ir-Cl(CO)(PMe<sub>2</sub>Ph)<sub>2</sub> are both at 1960 cm<sup>−1</sup>, whereas the υ<sub>CO</sub> for Ir-Cl(CO)(PMe<sub>3</sub>)<sub>2</sub> is at 1938 cm<sup>−1</sup>.<ref>S.A. Cotton, Chemistry of Precious Metals., 1997, 152-157, ISBN 0-7514-0413-6, ISBN 978-0-7514-0413-5</ref><ref>A.R. Norrris ; J.A.V. Kessel, ''Canadian Journal of Chemistry'', Oxidative addition of 3,5-Dinitrobenzoyl Chloride to trans-Chlorocarbonylbis(dimethylphenylphosphine)iridium(I), 1973, 51, 4145-4151, {{DOI|10.1139/CJC-51-24-4145}}.</ref> | |||
Also when comparing the acidity of HPR<sub>3</sub> (PR<sub>3</sub> = PMe<sub>2</sub>Ph, PPh<sub>3</sub>, PEt<sub>3</sub>) in CD<sub>2</sub>Cl<sub>2</sub>, the resulting [[pKa|pK<sub>a</sub>]] value is the following: [HPMe<sub>2</sub>Ph]<sup>+</sup>= 6.8, [HPPh<sub>3</sub>]<sup>+</sup> = 2.7, [HPEt<sub>3</sub>]<sup>+</sup> = 8.7.<ref>Russell C; Bush and Robert J. Angelici. Inorg. Chem, Phosphine Basicities As Determined by Enthalpies of Protonation 1988, 27, 681-686. {{doi|10.1021/ic00277a022}}</ref><ref>Tianshu Li ; Alan J.; Robert H., ''Chemistry- A European Journal'', An Acidity scale of Tetrafluoroborate Salts of Phosphonium and Iron Hydride compounds in [D2]Dichloromethane, 2007, volume 13, 3796-3803, {{DOI| 10.1002/chem..200601484}}.</ref> Thus PMe2Ph is intermediate in basicity relative to PPh<sub>3</sub> and PEt<sub>3</sub>. | |||
The ligand [[cone angle]] (θ) is the apex angle of a cylindrical cone, which is centered 2.28 Å from the center of the P atom. However, the cone angle of an unsymmetrical ligand cannot be determined in the same. In order to determine an effective cone angle for an unsymmetrical ligand PX<sub>1</sub>X<sub>2</sub>X<sub>3</sub>, the following equation is used: | |||
:<math>\theta = \frac{2}{3}\sum_{i=1}^3 \frac{\theta_i}2</math> | |||
Where θ<sub>i</sub> represent the half angle. | |||
The resulting angles for -PMe<sub>3</sub>, PMe<sub>2</sub>Ph, PPh<sub>3</sub> are the following: | |||
PMe<sub>3</sub>= 118°, PMe<sub>2</sub>Ph= 122°, PPh<sub>3</sub>= 145°. Thus PMe<sub>2</sub>Ph is intermediate in size relative to PMe<sub>3</sub> and PPh<sub>3</sub>.<ref>C.A.Tolman, ''Chem.Rev''., Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis., 1977, 313-348, {{DOI|10.1021/cr60307a002}}</ref> | |||
==References== | |||
{{Reflist}} | |||
[[Category:Tertiary phosphines]] | |||
[[Category:Aromatic compounds]] | |||
Revision as of 03:47, 21 September 2013
Template:Chembox Dimethylphenylphosphine is an organophosphorus compound with a formula P(C6H5)(CH3)2. The phosphorus is connected to a phenyl group and two methyl groups. This colorless air sensitive liquid is commonly used as a ligand in transition metal complexes. These complexes are often soluble in organic solvents.
Preparation
Dimethylphenylphosphine is prepared by the reaction of methylmagnesium halide with dichlorophenylphosphine.
- (C6H5)Cl2P + 2CH3MgBr → (C6H5)(CH3)2P + 2MgBrCl
The phosphine is purified by distillation under reduced pressure.[1] A solution of (C6H5)(CH3)2P in CDCl3 shows proton NMR signals at δ = 7.0-7.5 and a doublet at δ = 1.2. The phosphorus-31 NMR spectrum shows a singlet at -45.89 ppm in CDCl3.[2]
Structure and properties
Dimethylphenylphosphine is a pyramidal molecule where the phenyl group and two methyl groups are connected to the phosphorus. The bond length and angles are the following: P-CMe: 1.844, P-CPh: 1.845 Å, C-C: 1.401 Å, C-HMe: 1.090 Å, C-HPh: 1.067 Å, C-P-C: 96.9°, C-P-C (ring): 103.4°, P-C-H: 115.2°.[3]
The υCO of Ir-Cl(CO)(PPh3)2 and Ir-Cl(CO)(PMe2Ph)2 are both at 1960 cm−1, whereas the υCO for Ir-Cl(CO)(PMe3)2 is at 1938 cm−1.[4][5] Also when comparing the acidity of HPR3 (PR3 = PMe2Ph, PPh3, PEt3) in CD2Cl2, the resulting pKa value is the following: [HPMe2Ph]+= 6.8, [HPPh3]+ = 2.7, [HPEt3]+ = 8.7.[6][7] Thus PMe2Ph is intermediate in basicity relative to PPh3 and PEt3.
The ligand cone angle (θ) is the apex angle of a cylindrical cone, which is centered 2.28 Å from the center of the P atom. However, the cone angle of an unsymmetrical ligand cannot be determined in the same. In order to determine an effective cone angle for an unsymmetrical ligand PX1X2X3, the following equation is used:
Where θi represent the half angle.
The resulting angles for -PMe3, PMe2Ph, PPh3 are the following: PMe3= 118°, PMe2Ph= 122°, PPh3= 145°. Thus PMe2Ph is intermediate in size relative to PMe3 and PPh3.[8]
References
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- ↑ C. Frajerman; B. Meunier; M. E. Strem., Inorganic Syntheses, Preparation of Dimethylphenylphosphine, 2007, volume 22, 133-135, Electronic Instrument Positions Staff (Standard ) Cameron from Clarence Creek, usually spends time with hobbies and interests which include knotting, property developers in singapore apartment For sale and boomerangs. Has enrolled in a world contiki journey. Is extremely thrilled specifically about visiting .. ch29
- ↑ Laszlo T. Mika, Laszlo Orha, Norbert Farkas and Istvan T. Horvath, Organometallics, 2009, 28, 1593
- ↑ Novikov, V.P., Kolomeets, V.I., Syshchikov, Yu.N., Vilkov, L.V., Yarkov, A.V., Tsvetkov, E.N., Raevskii, O.A.: Zh. Strukt. Khim., J. Struc. Chem., Investigation of structure of dimethylphenylphosphine by means of gas-phase electron diffraction and vibrational spectroscopy, 1984, volume 25, No.5, 688. Electronic Instrument Positions Staff (Standard ) Cameron from Clarence Creek, usually spends time with hobbies and interests which include knotting, property developers in singapore apartment For sale and boomerangs. Has enrolled in a world contiki journey. Is extremely thrilled specifically about visiting .
- ↑ S.A. Cotton, Chemistry of Precious Metals., 1997, 152-157, ISBN 0-7514-0413-6, ISBN 978-0-7514-0413-5
- ↑ A.R. Norrris ; J.A.V. Kessel, Canadian Journal of Chemistry, Oxidative addition of 3,5-Dinitrobenzoyl Chloride to trans-Chlorocarbonylbis(dimethylphenylphosphine)iridium(I), 1973, 51, 4145-4151, Electronic Instrument Positions Staff (Standard ) Cameron from Clarence Creek, usually spends time with hobbies and interests which include knotting, property developers in singapore apartment For sale and boomerangs. Has enrolled in a world contiki journey. Is extremely thrilled specifically about visiting ..
- ↑ Russell C; Bush and Robert J. Angelici. Inorg. Chem, Phosphine Basicities As Determined by Enthalpies of Protonation 1988, 27, 681-686. 21 year-old Glazier James Grippo from Edam, enjoys hang gliding, industrial property developers in singapore developers in singapore and camping. Finds the entire world an motivating place we have spent 4 months at Alejandro de Humboldt National Park.
- ↑ Tianshu Li ; Alan J.; Robert H., Chemistry- A European Journal, An Acidity scale of Tetrafluoroborate Salts of Phosphonium and Iron Hydride compounds in [D2]Dichloromethane, 2007, volume 13, 3796-3803, Electronic Instrument Positions Staff (Standard ) Cameron from Clarence Creek, usually spends time with hobbies and interests which include knotting, property developers in singapore apartment For sale and boomerangs. Has enrolled in a world contiki journey. Is extremely thrilled specifically about visiting ..
- ↑ C.A.Tolman, Chem.Rev., Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis., 1977, 313-348, Electronic Instrument Positions Staff (Standard ) Cameron from Clarence Creek, usually spends time with hobbies and interests which include knotting, property developers in singapore apartment For sale and boomerangs. Has enrolled in a world contiki journey. Is extremely thrilled specifically about visiting .