Pentaphenylphosphorus

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Pentaphenylphosphorus
Pentaphenylphosphorus.svg
Names
IUPAC name
pentakis-phenyl-λ5-phosphane
Identifiers
  • 2588-88-7
3D model (JSmol)
ChemSpider
  • 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
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[]

  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. ^ 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.
  3. ^ 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.
  4. ^ 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(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.
  6. ^ 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.
  7. ^ 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.
  8. ^ 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.
  9. ^ 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.
  10. ^ 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[]

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