Pentaphenylphosphorus

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Pentaphenylphosphorus
Chemical structure of Ph5P.svg
Names
IUPAC name
pentakis-phenyl-λ5-phosphane
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/C30H25P/c1-6-16-26(17-7-1)31(27-18-8-2-9-19-27,28-20-10-3-11-21-28,29-22-12-4-13-23-29)30-24-14-5-15-25-30/h1-25H
    Key: YJOZRPLVYQSYCZ-UHFFFAOYSA-N
  • C1=CC=C(C=C1)P(C2=CC=CC=C2)(C3=CC=CC=C3)(C4=CC=CC=C4)C5=CC=CC=C5
Properties
C30H25P
Molar mass 416.504 g·mol−1
Appearancecolourless [1]
Density 1.22
Related compounds
Other cations
pentaphenylarsenic
pentaphenylantimony
pentaphenylbismuth
Related compounds
triphenylphosphine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Pentaphenylphosphorus is an organic phosphorane containing five phenyl groups connected to a central phosphorus atom. The phosphorus atom is considered to be in the +5 oxidation state. The chemical formula could be written as P(C6H5)5 or Ph5P, where Ph represents the phenyl group. It was discovered and reported in 1949 by Georg Wittig. [2]

Contents

Formation and history

Pentaphenylphosphorus can be formed by the action of phenyllithium on tetraphenylphosphonium bromide or tetraphenylphosphonium iodide. [3] . The compound was produced during the course of Wittig's Nobel-prize-winning investigations of organophosphorus compounds. [2]

Structure

Pentaphenylphosphorus is trigonal bipyramidal, according to several determinations by X-ray crystallography. The axial and equatorial P-C bond lengths are 199 and 185 picometers, respectively. [4]

The monoclinic crystal has dimensions a=10.03, b=17.22 c=14.17 Å and β=112.0°. [4] Pentaphenyl phosphorus can also crystallise with solvent, (to form a solvate) with tetrahydrofuran and cyclohexane. [5] [6]

Reactions

On heating, pentaphenylphosphorus decomposes to form biphenyl and triphenylphosphine. [2]

Pentaphenylphosphorus reacts with acidic hydrogen to yield the tetraphenylphosphonium ion and benzene. [2] For example pentaphenylphosphorus reacts with carboxylic acids and sulfonic acids to yield the tetraphenylphosphonium salt of the carboxylate or sulfonate, and benzene. [7]

Pentaphenylphosphorus transfers a phenyl group to organomercury, and tin halides. For example pentaphenylphosphorus reacts with phenylmercury chloride to yield diphenyl mercury and tetraphenylphosphonium chloride. With tributyltin chloride, tributylphenyltin is produced. However the pentaphenylphosphorus reaction with triphenylbismuth difluoride, chloride or bromide makes triphenylbismuth and fluorobenzene, chlorobenzene or bromobenzene. This is probably because tetraphenylbismuth halides (Ph4BiF, Ph4BiCl, Ph4BiBr) spontaneously decompose as the halogen reacts with one phenyl group. [8]

When heated with carbon dioxide or sulfur, bicyclic compounds are formed, where the reactant bridges between one of the phenyl groups and the phosphorus. [9]

Related Research Articles

<span class="mw-page-title-main">Ether</span> Organic compounds made of alkyl/aryl groups bound to oxygen (R–O–R)

In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula R−O−R′, where R and R′ represent the alkyl or aryl groups. Ethers can again be classified into two varieties: if the alkyl or aryl groups are the same on both sides of the oxygen atom, then it is a simple or symmetrical ether, whereas if they are different, the ethers are called mixed or unsymmetrical ethers. A typical example of the first group is the solvent and anaesthetic diethyl ether, commonly referred to simply as "ether". Ethers are common in organic chemistry and even more prevalent in biochemistry, as they are common linkages in carbohydrates and lignin.

<span class="mw-page-title-main">Anisole</span> Organic compound (CH₃OC₆H₅) also named methoxybenzene

Anisole, or methoxybenzene, is an organic compound with the formula CH3OC6H5. It is a colorless liquid with a smell reminiscent of anise seed, and in fact many of its derivatives are found in natural and artificial fragrances. The compound is mainly made synthetically and is a precursor to other synthetic compounds. Structurally, it is an ether with a methyl and phenyl group attached. Anisole is a standard reagent of both practical and pedagogical value.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

<span class="mw-page-title-main">Benzoyl chloride</span> Organochlorine compound (C7H5ClO)

Benzoyl chloride, also known as benzenecarbonyl chloride, is an organochlorine compound with the formula C7H5ClO. It is a colourless, fuming liquid with an irritating odour, and consists of a benzene ring with an acyl chloride substituent. It is mainly useful for the production of peroxides but is generally useful in other areas such as in the preparation of dyes, perfumes, pharmaceuticals, and resins.

<span class="mw-page-title-main">Phosphonium</span> Family of polyatomic cations containing phosphorus

In chemistry, the term phosphonium 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.

<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.

<span class="mw-page-title-main">Aromatic sulfonation</span> Chemical reaction which replaces a hydrogen on an arene with sulfonic acid, –NH–SO3H

In organic chemistry, aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution. Aryl sulfonic acids are used as detergents, dye, and drugs.

<span class="mw-page-title-main">Wilhelm Rudolph Fittig</span> German chemist (1835–1910)

Wilhelm Rudolph Fittig was a German chemist. He discovered the pinacol coupling reaction, mesitylene, diacetyl and biphenyl. Fittig studied the action of sodium on ketones and hydrocarbons. He discovered the Fittig reaction or Wurtz–Fittig reaction for the synthesis of alkylbenzenes, he proposed a diketone structure for benzoquinone and isolated phenanthrene from coal tar. He discovered and synthesized the first lactones and investigated structures of piperine, naphthalene, and fluorene.

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

Crotonic acid ((2E)-but-2-enoic acid) is a short-chain unsaturated carboxylic acid described by the formula CH3CH=CHCO2H. The name crotonic acid was given because it was erroneously thought to be a saponification product of croton oil. It crystallizes as colorless needles from hot water. With a cis-alkene, Isocrotonic acid is an isomer of crotonic acid. Crotonic acid is soluble in water and many organic solvents. Its odor is similar to that of butyric acid.

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.

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

Diphenylmethane is an organic compound with the formula (C6H5)2CH2 (often abbreviated CH
2
Ph
2
). The compound consists of methane wherein two hydrogen atoms are replaced by two phenyl groups. It is a white solid.

The Wurtz–Fittig reaction is the chemical reaction of an aryl halide, alkyl halides, and sodium metal to give substituted aromatic compounds. Following the work of Charles Adolphe Wurtz on the sodium-induced coupling of alkyl halides, Wilhelm Rudolph Fittig extended the approach to the coupling of an alkyl halide with an aryl halide. This modification of the Wurtz reaction is considered a separate process and is named for both scientists.

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

Diphenylketene is a chemical substance of the ketene family. Diphenylketene, like most stable disubstituted ketenes, is a red-orange oil at room temperature and pressure. Due to the successive double bonds in the ketene structure R1R2C=C=O, diphenyl ketene is a heterocumulene. The most important reaction of diphenyl ketene is the [2+2] cycloaddition at C-C, C-N, C-O, and C-S multiple bonds.

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

Sodium tetraphenylborate is the organic compound with the formula NaB(C6H5)4. It is a salt, wherein the anion consists of four phenyl rings bonded to boron. This white crystalline solid is used to prepare other tetraphenylborate salts, which are often highly soluble in organic solvents. The compound is used in inorganic and organometallic chemistry as a precipitating agent for potassium, ammonium, rubidium, and cesium ions, and some organic nitrogen compounds.

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

Triphenylborane, often abbreviated to BPh3 where Ph is the phenyl group C6H5-, is a chemical compound with the formula B(C6H5)3. It is a white crystalline solid and is both air and moisture sensitive, slowly forming benzene and triphenylboroxine. It is soluble in aromatic solvents.

<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">Phenylsodium</span> Chemical compound

Phenylsodium C6H5Na is an organosodium compound. Solid phenylsodium was first isolated by Nef in 1903. Although the behavior of phenylsodium and phenyl magnesium bromide are similar, the organosodium compound is very rarely used.

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

Dimethylcarbamoyl chloride (DMCC) is a reagent for transferring a dimethylcarbamoyl group to alcoholic or phenolic hydroxyl groups forming dimethyl carbamates, usually having pharmacological or pesticidal activities. Because of its high toxicity and its carcinogenic properties shown in animal experiments and presumably also in humans, dimethylcarbamoyl chloride can only be used under stringent safety precautions.

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

Pentamethylarsenic (or pentamethylarsorane)is an organometalllic compound containing five methyl groups bound to an arsenic atom with formula As(CH3)5. It is an example of a hypervalent compound. The molecular shape is trigonal bipyramid.

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

Pentaphenylantimony is an organoantimony compound containing five phenyl groups attached to one antimony atom. It has formula Sb(C6H5)5 (or SbPh5).

References

  1. Freeman, B.H.; Lloyd, D.; Singer, M.I.C. (January 1972). "Tetraphenylcyclopentadienylides". Tetrahedron. 28 (2): 343–352. doi:10.1016/0040-4020(72)80141-8.
  2. 1 2 3 4 Wittig, Georg; Rieber, Martin (1949-05-10). "Über die Metallierbarkeit von quaternären Ammonium- und Phosphonium-Salzen". Justus Liebigs Annalen der Chemie. 562 (3): 177–186. doi:10.1002/jlac.19495620303.
  3. Wittig, Georg; Rieber, Martin (1949). "Darstellung und Eigenschaften des Pentaphenyl-phosphors" [Preparation and Properties of Pentaphenyl-Phosphorus]. Justus Liebigs Annalen der Chemie. 562 (3): 187–192. doi:10.1002/jlac.19495620304.
  4. 1 2 Wheatley, P. J. (1964). "408. The Crystal and Molecular Structure of Pentaphenylphosphorus". Journal of the Chemical Society (Resumed): 2206. doi:10.1039/JR9640002206.
  5. Müller, Gerhard; Bildmann, Ulrich Jürgen (2004-12-01). "Crystal and Molecular Structure of P(C6H5)5·0.5THF". Zeitschrift für Naturforschung B. 59 (11–12): 1411–1414. doi:10.1515/znb-2004-11-1207. S2CID   99733089.
  6. Brock, C. P. (1977-11-01). "Lattice Energy Calculations for (C6H5)5M0.5C6H12, M = P, As and Sb: Towards an Understanding of Crystal Packing in the Pentaphenyl Group V Compounds". Acta Crystallographica Section A. 33 (6): 898–902. Bibcode:1977AcCrA..33..898B. doi:10.1107/S0567739477002204.
  7. Shaturin, V. V.; Senchurin, V. S.; Shaturina, O. K.; Boyarkina, E. A. (January 2009). "Tetraphenylphosphonium carboxylates and sulfonates. Synthesis and structure". Russian Journal of General Chemistry. 79 (1): 78–87. doi:10.1134/S1070363209010125. S2CID   96900890.
  8. Sharutin, V. V.; Sharutina, O. K.; Senchurin, V. S.; Egorova, I. V.; Ivanenko, T. K.; Petrov, B. I. (2003). "Phenylation of Organic Derivatives of Mercury, Silicon, Tin, and Bismuth with Pentaphenylantimony and Pentaphenylphosphorus". Russian Journal of General Chemistry. 73 (2): 202–203. doi:10.1023/A:1024731719528. S2CID   91420871.
  9. C. D. Hall (1990). "Pentaco-ordinated and Hexaco-ordinated Compounds". In B. J. Walker (ed.). Organophosphorus Chemistry. Royal Society of Chemistry. pp. 51–54. ISBN   978-0-85186-196-8.

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