Pentaphenylphosphorus
![]() | |
Names | |
---|---|
IUPAC name
pentakis-phenyl-λ5-phosphane
| |
Identifiers | |
| |
3D model (JSmol)
|
|
ChemSpider | |
PubChem CID
|
|
CompTox Dashboard (EPA)
|
|
| |
| |
Properties | |
C30H25P | |
Molar mass | 416.504 g·mol−1 |
Appearance | colourless[1] |
Density | 1.22 |
Related compounds | |
Other cations
|
pentaphenylantimony |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
Infobox references | |
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]
Formation[]
Pentaphenylphosphorus can be formed by the action of phenyllithium on [3] or .[2]
Properties[]
In the solid form of pure pentaphenylphosphorus, molecules have a trigonal bipyramid shape. The crystal structure of the pure form is monoclinic with a=10.03, b=17.22 c=14.17 Å and β=112.0°. The unit cell volume is 2267.5 Å3. There are four of the formula per unit cell (Z=4). Space group is Cc.[4] Pentaphenyl phosphorus can also crystallise with some of the solvent, (to form a solvate). With tetrahydrofuran, the crystal structure of which is triclinic, with space group P1, with unit cell dimensions a=10.095 b=10.252 c=12.725 Å α=71.21, β=76.98, γ=87.12 with Z=2.[5] It can also form a solvate crystal with cyclohexane[6] or benzene.[7]
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.[8]
Pentaphenylphosphorus transfers a phenyl group to organomercury, and tin halides. For example pentaphenylphosphorus reacts with to yield diphenyl mercury and tetraphenylphosphonium chloride. With tributyltin chloride, tributylphenyltin is produced. However the pentaphenylphosphorus reaction with , or makes and fluorobenzene, chlorobenzene or bromobenzene. This is probably because tetraphenylbismuth halides (Ph4BiF, Ph4BiCl, Ph4BiBr) spontaneously decompose as the halogen reacts with one phenyl group.[9]
When heated with carbon dioxide or sulfur, bicyclic compounds are formed, where the reactant bridges between one of the phenyl groups and the phosphorus.[10]
References[]
- ^ 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.
- ^ a b c d 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.
- ^ Seyferth, Dietmar.; Fogel, Joseph S.; Heeren, James K. (January 1964). "The Reaction of Vinyllithium with Tetraphenylphosphonium Bromide and the Formation of Phosphinemethylenes by RLi Addition to Vinylphosphonium Halides". Journal of the American Chemical Society. 86 (2): 307–308. doi:10.1021/ja01056a059.
- ^ Wheatley, P. J. (1964). "408. The crystal and molecular structure of pentaphenylphosphorus". Journal of the Chemical Society (Resumed): 2206. doi:10.1039/JR9640002206.
- ^ Müller, Gerhard; Bildmann, Ulrich Jürgen (2004-12-01). "Crystal and Molecular Structure of P(C 6 H 5 ) 5 · 0.5 THF". Zeitschrift für Naturforschung B. 59 (11–12): 1411–1414. doi:10.1515/znb-2004-11-1207. S2CID 99733089.
- ^ Brock, C. P. (1977-11-01). "Lattice energy calculations for (C 6 H 5 ) 5 M 0.5C 6 H 12 , 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.
- ^ Губанова, Юлия Олеговна; Шарутина, Ольга Константиновна (2020-08-16). "Синтез и строение карбоксилатов тетрафенилфосфония [Ph 4 P][OC(O)C 6 H 3 (OH) 2 -2,6], [Ph 4 P][OC(O)CH 2 CH 2 C(O)OH]" [Synthesis and Structure of Tetraphenylphosphonium Carboxylates [Ph4P][OC(O)C6H3 (OH) 2-2,6], [Ph4P][OC(O)CH2CH2C(O)OH]]. Химия (in Russian). 12 (3): 79–87.
- ^ 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.
- ^ 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.
- ^ 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.
Extra reading[]
- Zykova, A.R. (2021). "РЕАКЦИЯ ПЕНТАФЕНИЛФОСФОРА С ГЕКСАХЛОРОПЛАТИНОВОЙ КИСЛОТОЙ" [Reaction of Pentaphenylphosphorus with Hexachloroplatinic Acid]. Bulletin of the South Ural State University Series "Chemistry" (in Russian). 13 (1): 31–38. doi:10.14529/chem210103.
- Hoffmann, Roald; Howell, James M.; Muetterties, Earl L. (May 1972). "Molecular orbital theory of pentacoordinate phosphorus" (PDF). Journal of the American Chemical Society. 94 (9): 3047–3058. doi:10.1021/ja00764a028.
- Phosphorus(V) compounds
- Phenyl compounds