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]
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]
Structureedit
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]
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]
^ abcdWittig, 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.
^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.
^ abWheatley, 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(C6H5)5·0.5THF". 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 (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.
^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. ISBN978-0-85186-196-8.
Extra readingedit
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.
January 01, 1970
pentaphenylphosphorus, organic, phosphorane, containing, five, phenyl, groups, connected, central, phosphorus, atom, phosphorus, atom, considered, oxidation, state, chemical, formula, could, written, c6h5, ph5p, where, represents, phenyl, group, discovered, re. 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 Pentaphenylphosphorus Names IUPAC name pentakis phenyl l5 phosphane Identifiers CAS Number 2588 88 7 3D model JSmol Interactive image ChEBI CHEBI 194485 ChemSpider 2065130 PubChem CID 2785233 CompTox Dashboard EPA DTXSID60382874 InChI 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 25HKey YJOZRPLVYQSYCZ UHFFFAOYSA N SMILES C1 CC C C C1 P C2 CC CC C2 C3 CC CC C3 C4 CC CC C4 C5 CC CC C5 Properties Chemical formula C 30H 25P Molar mass 416 504 g mol 1 Appearance colourless 1 Density 1 22 Related compounds Other cations pentaphenylarsenicpentaphenylantimonypentaphenylbismuth Related compounds triphenylphosphine Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Formation and history 2 Structure 3 Reactions 4 References 5 Extra readingFormation and history editPentaphenylphosphorus 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 editPentaphenylphosphorus 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 A and b 112 0 4 Pentaphenyl phosphorus can also crystallise with solvent to form a solvate with tetrahydrofuran and cyclohexane 5 6 Reactions editOn 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 References edit 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 Uber die Metallierbarkeit von quaternaren Ammonium und Phosphonium Salzen Justus Liebigs Annalen der Chemie 562 3 177 186 doi 10 1002 jlac 19495620303 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 a b Wheatley P J 1964 408 The Crystal and Molecular Structure of Pentaphenylphosphorus Journal of the Chemical Society Resumed 2206 doi 10 1039 JR9640002206 Muller Gerhard Bildmann Ulrich Jurgen 2004 12 01 Crystal and Molecular Structure of P C6H5 5 0 5THF Zeitschrift fur 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 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 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 editZykova A R 2021 REAKCIYa PENTAFENILFOSFORA S GEKSAHLOROPLATINOVOJ KISLOTOJ 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 Retrieved from https en wikipedia org w index php title Pentaphenylphosphorus amp oldid 1208877826, wikipedia, wiki, book, books, library,
