Artikel
Lizenziert
Nicht lizenziert
Erfordert eine Authentifizierung
Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren
-
Skeletal Rearrangements
Veröffentlicht/Copyright:
2. Juni 2014
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
Sie haben derzeit keinen Zugang zu diesem Inhalt.
Sie haben derzeit keinen Zugang zu diesem Inhalt.
Artikel in diesem Heft
- 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)- germatranes. Synthesis, Characterisation, and Crystal Structures
- Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes
- Solventothermal Synthesis and Structure of the Polymerie Thioarsenates(III) (Et4N)2As6S10 and (Et4N)2As8S13
- Cleavage and Formation of P-C Bonds During an Unusual Kinnear-Perren Reaction
- 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)]
- Synthesis and Molecular Structure of a Superbulky Tertiary Phosphine: Bis[2-phenyl-1,2-dicarba-closo-dodecaboran-1-yl(12)]phenylphosphine
- Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
- Structure and Magnetic Properties of an Oxalic Acid Bridged Dinuclear Copper(II) Complex
- Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren
- Ligand Redistribution Equilibria in Aqueous Fluoroberyllate Solutions
- Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene
- 2-Diphenylphosphino-phenoI as a Ligand for Mono- and Poly-Nuclear Complexes of Manganese, Cobalt, Nickel, Zinc, and Cadmium
- Isolation and Structural Characterisation of Monoprotonated 1,2-Bis(diphenylphosphino)benzene in its Tetrabromogallate(III) Salt
- 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
- Crystal Structure of Pyridinium Periodate
- 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
- 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
- Darstellung und Kristallstruktur von /wer-[Os(NCS)3Py3] / Synthesis and Crystal Structure of mer-[Os(NCS)3Py3]
- 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-
- Thermochemisches und kalorisches Verhalten von NdAl3Cl12 / Thermochemical and Calorical Behaviour of NdAl3Cl12
- Untersuchungen zum thermischen Verhalten der Osmiumoxide / Investigation of the Thermochemical Behaviour of Osmium Oxides
- Metal Complexes of Biologically Important Ligands, CVII [1], Formation of Tris(pentamethylcyclopentadienyl-μ-L-prolinato-iridium) Tris(trifluoromethanesulfonate) with Chiral Self Recognition
- 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
- Nickel Complexes of N-Alkylated Derivatives of 2,6-Bis(aminomethyl)- 4-tert-butyl-thiophenol
- The Molecular Structure of Tris(dimethylstibino)amine
Schlagwörter für diesen Artikel
Phosphonium Ylides;
Halophosphanes;
Chloride Abstraction;
Skeletal Rearrangement;
Tetraphospha-bicyclooctanes
Artikel in diesem Heft
- 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)- germatranes. Synthesis, Characterisation, and Crystal Structures
- Synthesis and Characterization of 1-Allyl-3,7,10-trimethylgermatrane and 1-Allylazagermatranes
- Solventothermal Synthesis and Structure of the Polymerie Thioarsenates(III) (Et4N)2As6S10 and (Et4N)2As8S13
- Cleavage and Formation of P-C Bonds During an Unusual Kinnear-Perren Reaction
- 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)]
- Synthesis and Molecular Structure of a Superbulky Tertiary Phosphine: Bis[2-phenyl-1,2-dicarba-closo-dodecaboran-1-yl(12)]phenylphosphine
- Synthesis of Glycosyl Cyanides by the Reaction of 1-S-Phosphorothioates of Carbohydrates with Trimethylsilyl Cyanide
- Structure and Magnetic Properties of an Oxalic Acid Bridged Dinuclear Copper(II) Complex
- Gerüstumlagerungen bei einem Yliddiylphosphan-Tetrameren
- Ligand Redistribution Equilibria in Aqueous Fluoroberyllate Solutions
- Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenylphosphino) ethene
- 2-Diphenylphosphino-phenoI as a Ligand for Mono- and Poly-Nuclear Complexes of Manganese, Cobalt, Nickel, Zinc, and Cadmium
- Isolation and Structural Characterisation of Monoprotonated 1,2-Bis(diphenylphosphino)benzene in its Tetrabromogallate(III) Salt
- 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
- Crystal Structure of Pyridinium Periodate
- 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
- 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
- Darstellung und Kristallstruktur von /wer-[Os(NCS)3Py3] / Synthesis and Crystal Structure of mer-[Os(NCS)3Py3]
- 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-
- Thermochemisches und kalorisches Verhalten von NdAl3Cl12 / Thermochemical and Calorical Behaviour of NdAl3Cl12
- Untersuchungen zum thermischen Verhalten der Osmiumoxide / Investigation of the Thermochemical Behaviour of Osmium Oxides
- Metal Complexes of Biologically Important Ligands, CVII [1], Formation of Tris(pentamethylcyclopentadienyl-μ-L-prolinato-iridium) Tris(trifluoromethanesulfonate) with Chiral Self Recognition
- 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
- Nickel Complexes of N-Alkylated Derivatives of 2,6-Bis(aminomethyl)- 4-tert-butyl-thiophenol
- The Molecular Structure of Tris(dimethylstibino)amine
