1,2-Bis(diphenylphosphino)ethane

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1,2-Bis(diphenylphosphino)ethane
DPPE structure.svg
Dppe-from-xtal-2001-3D-balls.png
Names
Preferred IUPAC name
(Ethane-1,2-diyl)bis(diphenylphosphane)
Other names
1,2-Bis(diphenylphosphino)ethane
Diphos
Dppe
Identifiers
3D model (JSmol)
761261
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.015.246 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 216-769-2
9052
PubChem CID
UNII
  • InChI=1S/C26H24P2/c1-5-13-23(14-6-1)27(24-15-7-2-8-16-24)21-22-28(25-17-9-3-10-18-25)26-19-11-4-12-20-26/h1-20H,21-22H2 Yes check.svgY
    Key: QFMZQPDHXULLKC-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C26H24P2/c1-5-13-23(14-6-1)27(24-15-7-2-8-16-24)21-22-28(25-17-9-3-10-18-25)26-19-11-4-12-20-26/h1-20H,21-22H2
    Key: QFMZQPDHXULLKC-UHFFFAOYAX
  • P(c1ccccc1)(c2ccccc2)CCP(c3ccccc3)c4ccccc4
  • c1ccc(cc1)P(CCP(c2ccccc2)c3ccccc3)c4ccccc4
Properties
C26H24P2
Molar mass 398.42 g/mol
Melting point 140 to 142 °C (284 to 288 °F; 413 to 415 K)
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H302, H315, H319, H332, H335, H410
P261, P264, P270, P271, P273, P280, P301+P312, P302+P352, P304+P312, P304+P340, P305+P351+P338, P312, P321, P330, P332+P313, P337+P313, P362, P391, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

1,2-Bis(diphenylphosphino)ethane (dppe) is an organophosphorus compound with the formula (Ph2PCH2)2 (Ph = phenyl). It is a common symmetrical bidentate ligand in coordination chemistry. It is a white solid that is soluble in organic solvents.

Contents

Preparation

The preparation of dppe entails the alkylation of NaP(C6H5)2 with 1,2-dichloroethane: [1] [2]

2 NaP(C6H5)2 + ClCH2CH2Cl → (C6H5)2PCH2CH2P(C6H5)2 + 2 NaCl

Reactions

The reduction of dppe by lithium give the disecondary phosphine: [3]

(C6H5)2PCH2CH2P(C6H5)2 4 Li → Li(C6H5)PCH2CH2P(C6H5)Li + 2 C6H5Li

Hydrolysis gives the bis(secondary phosphine).

Li(C6H5)PCH2CH2P(C6H5)Li + 2 H2O → H(C6H5)PCH2CH2P(C6H5)H + 2 LiOH
The bis(dppe) complex HFeCl(dppe)2 is one of the most accessible transition metal hydrides. HFeCl dppe 2.svg
The bis(dppe) complex HFeCl(dppe)2 is one of the most accessible transition metal hydrides.

Treatment of dppe with hydrogen peroxide pproduces the phosphine oxides (C6H5)2P(O)CH2CH2P(C6H5)2 and (C6H5)2P(O)CH2CH2P(O)(C6H5)2. [4] Selective mono-oxidation of dppe can be achieved by benzylation followed by hydrolysis:

(C6H5)2PCH2CH2P(C6H5)2 + C6H5CH2Br → (C6H5)2PCH2CH2P(C6H5)2(CH2C6H5)]Br
(C6H5)2PCH2CH2P(C6H5)2(CH2C6H5)]Br + NaOH → (C6H5)2PCH2CH2P(O)(C6H5)2 + C6H5CH3 + NaBr

Hydrogenation of dppe gives the ligand bis(dicyclohexylphosphino)ethane.

Coordination complexes

Many coordination complexes of dppe are known, and some are used as homogeneous catalysts. Dppe is almost invariably chelating, although there are examples of monodentate (e.g., W(CO)5(dppe)) and of bridging behavior. [5] The natural bite angle is 86°. [6]

Related Research Articles

<span class="mw-page-title-main">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an 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.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

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).

<span class="mw-page-title-main">1,1'-Bis(diphenylphosphino)ferrocene</span> Chemical compound

1,1-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an organophosphorus compound commonly used as a ligand in homogeneous catalysis. It contains a ferrocene moiety in its backbone, and is related to other bridged diphosphines such as 1,2-bis(diphenylphosphino)ethane (dppe).

<span class="mw-page-title-main">Diphosphine ligands</span>

Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts.

<span class="mw-page-title-main">Diphenylphosphine</span> Chemical compound

Diphenylphosphine, also known as diphenylphosphane, is an organophosphorus compound with the formula (C6H5)2PH. This foul-smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as catalysts.

Phenylphosphine is an organophosphorus compound with the chemical formula C6H5PH2. It is the phosphorus analog of aniline. Like other primary phosphines, phenylphosphine has an intense penetrating odor and is highly oxidizable. It is mainly used as a precursor to other organophosphorus compounds. It can function as a ligand in coordination chemistry.

<span class="mw-page-title-main">Bis(diphenylphosphino)methane</span> Chemical compound

1,1-Bis(diphenylphosphino)methane (dppm), is an organophosphorus compound with the formula CH2(PPh2)2. Dppm, a white, crystalline powder, is used in inorganic and organometallic chemistry as a ligand. It is more specifically a chelating ligand because it is a ligand that can bond to metals with two phosphorus donor atoms. The natural bite angle is 73°.

<span class="mw-page-title-main">1,3-Bis(diphenylphosphino)propane</span> Chemical compound

1,3-Bis(diphenylphosphino)propane (dppp) is an organophosphorus compound with the formula Ph2P(CH2)3PPh2. The compound is a white solid that is soluble in organic solvents. It is slightly air-sensitive, degrading in air to the phosphine oxide. It is classified as a diphosphine ligand in coordination chemistry and homogeneous catalysis.

<span class="mw-page-title-main">Dimethylphenylphosphine</span> Chemical compound

Dimethylphenylphosphine is an organophosphorus compound with a formula P(C6H5)(CH3)2. The phosphorus is connected to a phenyl group and two methyl groups, making it the simplest aromatic alkylphosphine. It is colorless air sensitive liquid. It is a member of series (CH3)3-n(C6H5)2P that also includes n = 0, n = 2, and n = 3 that are often employed as ligands in metal phosphine complexes.

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

<span class="mw-page-title-main">Bis(dinitrogen)bis(1,2-bis(diphenylphosphino)ethane)molybdenum(0)</span> Chemical compound

trans-Bis(dinitrogen)bis[1,2-bis(diphenylphosphino)ethane]molybdenum(0) is a coordination complex with the formula Mo(N2)2(dppe)2. It is a relatively air stable yellow-orange solid. It is notable as being the first discovered dinitrogen containing complex of molybdenum.

<span class="mw-page-title-main">Chlorobis(dppe)iron hydride</span> 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.

<span class="mw-page-title-main">Diphenylphosphine oxide</span> Chemical compound

Diphenylphosphine oxide is an organophosphorus compound with the formula (C6H5)2P(O)H. It is a white solid that soluble in polar organic solvents.

<span class="mw-page-title-main">Diethylphosphite</span> Chemical compound

Diethyl phosphite 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. Diethyl phosphite is a colorless liquid. The molecule is tetrahedral.

<span class="mw-page-title-main">1,4-Bis(diphenylphosphino)butane</span> Chemical compound

1,4-Bis(diphenylphosphino)butane (dppb) is an organophosphorus compound with the formula (Ph2PCH2CH2)2. It is less commonly used in coordination chemistry than other diphosphine ligands such as dppe. It is a white solid that is soluble in organic solvents.

<span class="mw-page-title-main">Dichloro(1,2-bis(diphenylphosphino)ethane)nickel</span> Chemical compound

Dichloro[1,2-bis(diphenylphosphino)ethane]nickel is a coordination complex with the formula NiCl2(dppe); where dppe is the diphosphine 1,2-bis(diphenylphosphino)ethane. It is used as a reagent and as a catalyst. The compound is a bright orange-red diamagnetic solid. The complex adopts a square planar geometry.

Phosphanides are chemicals containing the [PH2] anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).

<span class="mw-page-title-main">Transition metal complexes of phosphine oxides</span>

Transition metal complexes of phosphine oxides are coordination complex containing one or more phosphine oxide ligands. Many phosphine oxides exist and most behave as hard Lewis bases. Almost invariably, phosphine oxides bind metals by formation of M-O bonds.

References

  1. W. Hewertson and H. R. Watson (1962). "283. The preparation of di- and tri-tertiary phosphines". J. Chem. Soc. : 1490–1494. doi:10.1039/JR9620001490.
  2. Girolami, G.; Rauchfuss, T.; Angelici, R. Synthesis and Technique in Inorganic Chemistry, 3rd ed.; University Science Books: Sausalito, CA, 1999; pp. 85-92. ISBN   0-935702-48-2
  3. Dogan, J.; Schulte, J.B.; Swiegers, G.F.; Wild, S.B. (2000). "Mechanism of Phosphorus-Carbon Bond Cleavage by Lithium in Tertiary Phosphines. An Optimized Synthesis of 1, 2-Bis (phenylphosphino) ethane". J. Org. Chem. 65 (4): 951–957. doi:10.1021/jo9907336. PMID   10814038.
  4. Encyclopedia of Reagents for Organic Synthesis 2001 John Wiley & Sons, Ltd
  5. Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry: A Comprehensive Text, 4th ed.; Wiley-Interscience Publications: New York, NY, 1980; p.246. ISBN   0-471-02775-8
  6. Birkholz (née Gensow), Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). "Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions". Chemical Society Reviews. 38 (4): 1099–1118. doi:10.1039/B806211K. PMID   19421583.