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Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren

  • Skeletal Rearrangements , Ylidediylphosphane Tetramer , Hans-Peter Schrödel , Alfred Schmidpeter and Heinrich Nöth
Published/Copyright: June 2, 2014
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 11

Condensation of the bis(trimethylsilyl)ylide Ph3PC(SiMe3)2 with PX3 (X = Cl, Br) yields the ionic tetramers 4a,b of ylidediyl-halophosphanes. Their cations (Ph3PC)4P4X3+ possess a tetraphosphabicyclo[2.2.2]octane (or tetraphospha-barrelane) skeleton ([AC]3BD spin system in 31P NMR spectra). Reaction of 4a with AlCl3 or GaCl3 converts the singly charged cation into the tetracation (Ph3PC)4P44+ having a cubane structure ([AB]4 spin system in the 31P NMR spectum). SbCl5 oxidizes 4a to give the dication (Ph3PC)4P4Cl42+ (counter ion: SbCl52-) with the barrelane skeleton either preserved (7) or rearranged into a tetraphospha-bicylco[3.3.0]- octane structure 8. In the latter case the dication contains a central diphosphanedionium bridge. Replacement of a chloro-substituent in 4a by an amino group also gives rise to a further dissociation and a concomitant rearrangement. The resulting dications (Ph3PC)4P4NR2Cl2+ possess a tetraphospha-bicyclo-[3.2.1]octane structure (with eight nonequivalent phosphorus atoms).

Keywords: Phosphonium Ylides; Halophosphanes; Chloride Abstraction; Skeletal Rearrangement; Tetraphospha-bicyclooctanes
Received: 1998-6-22
Published Online: 2014-6-2
Published in Print: 1998-11-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)- germatranes. Synthesis, Characterisation, and Crystal Structures
  2. Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes
  3. Solventothermal Synthesis and Structure of the Polymerie Thioarsenates(III) (Et4N)2As6S10 and (Et4N)2As8S13
  4. Cleavage and Formation of P-C Bonds During an Unusual Kinnear-Perren Reaction
  5. Mechanistische Untersuchungen zum reversiblen Gleichgewicht von metallorganischen Tripeldecker- und Sandwichkomplexen des Typs [Bis{(η5-CpR)Co}-μ-{η4:η4-aren}] und [(η5-CpR)Co(η6-aren)] / Mechanistic Studies towards the Reversible Equilibrium between Metal Organic Triple Decker and Sandwich Complexes [Bis{(η5 -CpR)Co}-μ-{η4 :η4-arene}] and [{(η5-CpR)Co(η6-arene)]
  6. Synthesis and Molecular Structure of a Superbulky Tertiary Phosphine: Bis[2-phenyl-1,2-dicarba-closo-dodecaboran-1-yl(12)]phenylphosphine
  7. Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
  8. Structure and Magnetic Properties of an Oxalic Acid Bridged Dinuclear Copper(II) Complex
  9. Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren
  10. Ligand Redistribution Equilibria in Aqueous Fluoroberyllate Solutions
  11. Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene
  12. 2-Diphenylphosphino-phenoI as a Ligand for Mono- and Poly-Nuclear Complexes of Manganese, Cobalt, Nickel, Zinc, and Cadmium
  13. Isolation and Structural Characterisation of Monoprotonated 1,2-Bis(diphenylphosphino)benzene in its Tetrabromogallate(III) Salt
  14. Elementorganische Verbindungen mit o-Phenylenresten, XXXI [1]. Charge-transfer-Komplexe von 2,3,7,8-Tetrakis(methylthio)chalkogenanthrenen mit 7,7,8,8-Tetracyanchinodimethan und Tetracyanethen / Organometalloidal Compounds with o-Phenylene Substituents, Part XXXI [1]. Charge-transfer Complexes of 2,3,7,8-Tetrakis(methylthio)chalkogenanthrenes with 7,7,8,8-Tetracyanoquinodimethane and Tetracyanoethene
  15. Crystal Structure of Pyridinium Periodate
  16. Darstellung und Kristallstruktur von Bis(triphenylphosphin)-decahydro-hypho-hexaboran [(PPh3)2B6H10]·CH2Cl2 / Synthesis and Crystal Structure of Bis(triphenylphosphine)-decahydro-hypho-hexaborane[( PPh3)2B6H10]CH2Cl2
  17. Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-[ReCl4X2]2-, X = NCS, NCSe / Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of cis-[ReCl4X2]2-, X = NCS, NCSe
  18. Darstellung und Kristallstruktur von /wer-[Os(NCS)3Py3] / Synthesis and Crystal Structure of mer-[Os(NCS)3Py3]
  19. Darstellung, Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von trans-[OsO2(N2H2C2O2)2]2- / Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans-[OsO2(N2H2C202)2]2-
  20. Thermochemisches und kalorisches Verhalten von NdAl3Cl12 / Thermochemical and Calorical Behaviour of NdAl3Cl12
  21. Untersuchungen zum thermischen Verhalten der Osmiumoxide / Investigation of the Thermochemical Behaviour of Osmium Oxides
  22. Metal Complexes of Biologically Important Ligands, CVII [1], Formation of Tris(pentamethylcyclopentadienyl-μ-L-prolinato-iridium) Tris(trifluoromethanesulfonate) with Chiral Self Recognition
  23. Nachbargruppenbeteiligung bei der Dehydrierung cyclischer Amine vom Typ o-substituierter Anilinderivate / Neighbourgroup Participation with the Dehydrogenation of Cyclic Amines of the o-Substituted Aniline Type
  24. Nickel Complexes of N-Alkylated Derivatives of 2,6-Bis(aminomethyl)- 4-tert-butyl-thiophenol
  25. The Molecular Structure of Tris(dimethylstibino)amine
https://doi.org/10.1515/znb-1998-1109
Keywords for this article
Phosphonium Ylides; Halophosphanes; Chloride Abstraction; Skeletal Rearrangement; Tetraphospha-bicyclooctanes

Articles in the same Issue

  1. 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)- germatranes. Synthesis, Characterisation, and Crystal Structures
  2. Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes
  3. Solventothermal Synthesis and Structure of the Polymerie Thioarsenates(III) (Et4N)2As6S10 and (Et4N)2As8S13
  4. Cleavage and Formation of P-C Bonds During an Unusual Kinnear-Perren Reaction
  5. Mechanistische Untersuchungen zum reversiblen Gleichgewicht von metallorganischen Tripeldecker- und Sandwichkomplexen des Typs [Bis{(η5-CpR)Co}-μ-{η4:η4-aren}] und [(η5-CpR)Co(η6-aren)] / Mechanistic Studies towards the Reversible Equilibrium between Metal Organic Triple Decker and Sandwich Complexes [Bis{(η5 -CpR)Co}-μ-{η4 :η4-arene}] and [{(η5-CpR)Co(η6-arene)]
  6. Synthesis and Molecular Structure of a Superbulky Tertiary Phosphine: Bis[2-phenyl-1,2-dicarba-closo-dodecaboran-1-yl(12)]phenylphosphine
  7. Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
  8. Structure and Magnetic Properties of an Oxalic Acid Bridged Dinuclear Copper(II) Complex
  9. Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren
  10. Ligand Redistribution Equilibria in Aqueous Fluoroberyllate Solutions
  11. Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene
  12. 2-Diphenylphosphino-phenoI as a Ligand for Mono- and Poly-Nuclear Complexes of Manganese, Cobalt, Nickel, Zinc, and Cadmium
  13. Isolation and Structural Characterisation of Monoprotonated 1,2-Bis(diphenylphosphino)benzene in its Tetrabromogallate(III) Salt
  14. Elementorganische Verbindungen mit o-Phenylenresten, XXXI [1]. Charge-transfer-Komplexe von 2,3,7,8-Tetrakis(methylthio)chalkogenanthrenen mit 7,7,8,8-Tetracyanchinodimethan und Tetracyanethen / Organometalloidal Compounds with o-Phenylene Substituents, Part XXXI [1]. Charge-transfer Complexes of 2,3,7,8-Tetrakis(methylthio)chalkogenanthrenes with 7,7,8,8-Tetracyanoquinodimethane and Tetracyanoethene
  15. Crystal Structure of Pyridinium Periodate
  16. Darstellung und Kristallstruktur von Bis(triphenylphosphin)-decahydro-hypho-hexaboran [(PPh3)2B6H10]·CH2Cl2 / Synthesis and Crystal Structure of Bis(triphenylphosphine)-decahydro-hypho-hexaborane[( PPh3)2B6H10]CH2Cl2
  17. Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-[ReCl4X2]2-, X = NCS, NCSe / Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of cis-[ReCl4X2]2-, X = NCS, NCSe
  18. Darstellung und Kristallstruktur von /wer-[Os(NCS)3Py3] / Synthesis and Crystal Structure of mer-[Os(NCS)3Py3]
  19. Darstellung, Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von trans-[OsO2(N2H2C2O2)2]2- / Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans-[OsO2(N2H2C202)2]2-
  20. Thermochemisches und kalorisches Verhalten von NdAl3Cl12 / Thermochemical and Calorical Behaviour of NdAl3Cl12
  21. Untersuchungen zum thermischen Verhalten der Osmiumoxide / Investigation of the Thermochemical Behaviour of Osmium Oxides
  22. Metal Complexes of Biologically Important Ligands, CVII [1], Formation of Tris(pentamethylcyclopentadienyl-μ-L-prolinato-iridium) Tris(trifluoromethanesulfonate) with Chiral Self Recognition
  23. Nachbargruppenbeteiligung bei der Dehydrierung cyclischer Amine vom Typ o-substituierter Anilinderivate / Neighbourgroup Participation with the Dehydrogenation of Cyclic Amines of the o-Substituted Aniline Type
  24. Nickel Complexes of N-Alkylated Derivatives of 2,6-Bis(aminomethyl)- 4-tert-butyl-thiophenol
  25. The Molecular Structure of Tris(dimethylstibino)amine
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