Home Onio-assistierte SN2-Reaktionen: Allgemeiner Zugang zu symmetrischen und unsymmetrischen geminal bisoniosubstituierten Methanderivaten / Onio-Assisted SN2-Reactions: General Access to Symmetrical and Unsymmetrical Geminally Bisonio Substituted Methane Derivatives
Article
Licensed
Unlicensed Requires Authentication

Onio-assistierte SN2-Reaktionen: Allgemeiner Zugang zu symmetrischen und unsymmetrischen geminal bisoniosubstituierten Methanderivaten / Onio-Assisted SN2-Reactions: General Access to Symmetrical and Unsymmetrical Geminally Bisonio Substituted Methane Derivatives

  • Robert Weiss , Matthias Handke , Silvia Reichel and Frank Hampel
Published/Copyright: June 2, 2014
Become an author with De Gruyter Brill
Author Information Explore this Subject
Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 5-6

Abstract

The arsonium salt [Ph3As-CH2-OTf]+ OTf- 11a contains a 1,1-biselectrophilic Csp3 center which permits to synthesize a wide range of symmetrical and unsymmetrical geminally bisonio-substituted methane derivatives. With neutral nucleophiles INu under mild condi- tions a series of 1.1-bisonium salts [Ph3As-CH2-Nu]2+ 2OTf- 12-23 is obtained in good yields. Under more stringent conditions the triphenylarsonio function in these salts can also be mobilized as a nucleofuge in a subsequent SN-reaction with a second nucleophile | Nu’, yielding a series of novel unsymmetrical 1,1-bisonium salts [Nu-CH2-Nu’]2+ 2OTf- 24-27. Structures 18, 23 and 26b were confirmed by X-ray analysis. For certain nucleophiles a discrete stepwise substitution of both nucleofuges in 11a cannot be realized and the corresponding symmetrical 1,1-bisonium salts (e.g. 28 and 30-32) are obtained directly. The experimental material can be rationalized on the basis of a simple MO model. The conclusion is that stabilization of a hypervalent SN2 transition state by an equatorial oniosubstituent parallels the stability of the underlying ylids. This is corroborated by model calculations. The geminal bisonium salts reported are potential precursors to mono- and 1,1-bisylids and, in special cases, to functional nucleophilic carbenes.

Keywords: Geminal Bisonium Salts; SN-Reactions; Electrostatic Effects; Synthesis; X -Ray Data
Received: 1998-1-19
Published Online: 2014-6-2
Published in Print: 1998-6-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. Darstellung und Strukturbeschreibung von NaCa3 Mn(V2O7)(V3O10) / Preparation and Structure of NaCa3Mn(V2O7)(V3O10)
  2. Ba4Mn2Ag2O(As04)4 , ein Barium-Mangan-Oxid-Arsenat mit nichtlinearen O-Ag-O-Hanteln / Ba4Mn2Ag2O(AsO4)4, a Barium Manganese Oxide-Arsenate Showing Nonlinear O-Ag-O Dumbbells
  3. Indium partiell in tetraedrischer Sauerstoffkoordination in BaIn2Zn3O7. Eine Betrachtung zum Ba2Ln2Zn8O13/BaLnAlZn3O7 -Typ / Partial Tetrahedral Oxygen Coordination of Indium in BaIn2Zn3O7. A Consideration of the Ba2Ln2Zn8O13/BaLnAlZn3O7 Type
  4. Zur Kenntnis eines Vanadyl-Oxocuprat-Phosphats CaCu(VO)(PO4)2 mit Cu2+ auf Positionen der VO2+-Ionen und einer kupferreicheren Phase CaCu1,13(VO)0,87(PO4)2 / On an Vanadyl Oxocuprate Phosphate CaCu(VO)(PO4)2 Containing Cu2+ at Positions of VO2+ Ions and a Copper Rich Phase CaCu1.13(VO)0.87(PO4)2
  5. Verknüpfung von (TeO6)6- und (TeO6)3(NiO6)3-Sechsringen durch TeNiO9-Oktaederdoppel in Pb3Ni4,5Te2,5O15 / Connection of (TeO6)6 and (TeO6)3(NiO6)3 Hexagons by TeNiO9 Octahedra Double in Pb3Ni4,5Te2,5O15
  6. Preparation and X-Ray Structure of 3,5-Dimethyl-1,4-dichloro-1,2,6- thiadiazine-1-oxide
  7. Pentafluoro[(4-methyl-1,4-bisazoniacy clohex-1 -yl)methy 1] germanate Hydrate: Synthesis and Crystal Structure of a Zwitterionic λ6Ge-Germanate with a GeF5C Framework
  8. Mesitylene Osmium(II) Complexes Containing the Functional Phosphane tBuP(CH2CO2Me)2 and Anionic Species Derived Thereof as Bi- and Tridentate Ligands
  9. Benzylgallium-Verbindungen. Die Kristallstrukturen von [Mg3Br2,4Cl1,6(OEt2)6][Ga(CH2Ph)4]2 · 0,5 Toluol und [(3,5-Me2C6H3CH2)2GaBr]2 / Benzylgallium Compounds. The Crystal Structures of [Mg3Br2,4Cl1,6(OEt2)6][Ga(CH2Ph)4]2 · 0.5 Toluene and [(3,5-Me2C6H3CH2)2GaBr]2
  10. Die Kristallstruktur von [Me3PN(H)PMe3]4l28, einem Polyiodid mit I3--, l82-- und I144--Ionen Crystal / Structure of [Me3PN(H)PMe3]4I28, a Polyiodide with I3-, I82- , and I 144- Ions
  11. In situ Neutron Diffraction on DxNb2O5
  12. The First Hydrogen Containing (Polyfluorocycloalken-l-yl)xenon(II) Salts
  13. Kristallstruktur von 1,1'-Dimethyl-4,4'-bipyridinium-octachlorodiantimonat(III) / Crystal Structure of 1,1'-Dimethyl-4,4'-bipyridinium-octachlorodiantimonate(III)
  14. Kristallstruktur des Doppelkomplexsalzes trans-(py2CH2)[Pt(OH)2(ox)2]transs-(py2CH2)[Pt(OH)(ox)2(H2O)]2·4H2O / Crystal Structure of the Double Complex Salt trans-(py2CH2)[Pt(OH)2(ox)2](H2O)]2·4H2O
  15. Tetrakis(sulfurdiimido)silane, -germane and -stannane
  16. Synthese und Charakterisierung von kronenetherstabilisierten Platin(IV)- Komplexen mit Aminosäureliganden / Synthesis and Characterization of Amino Acid Complexes of Platinum(IV) Stabilized by Crown Ethers
  17. Hydrido(acylphenolato)cobaIt(III)-Verbindungen mit Trimethylphosphan-Liganden / Hydrido(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands
  18. Onio-assistierte SN2-Reaktionen: Allgemeiner Zugang zu symmetrischen und unsymmetrischen geminal bisoniosubstituierten Methanderivaten / Onio-Assisted SN2-Reactions: General Access to Symmetrical and Unsymmetrical Geminally Bisonio Substituted Methane Derivatives
  19. Anodic Methoxylation of Isatin
  20. Neuartige Synthese und Molekülstruktur von Benzylkalium (thf) [KCH2C6H5]2 / Novel Synthesis and Molecular Structure of Benzyl Potassium (thf)[KCH2C6H5]2
  21. Weitere Verbindungen zum Ba6Nd2Al4O15-Typ: Ba4Nd4Zn3PtO15 und Ba4Eu4Zn3PtO15 / Further Compounds of the Ba6Nd2Al4O15 Type: Ba4Nd4Zn3PtO15 and Ba4Eu4Zn3PtO15
  22. Fe[B2P2O7(OH)5]: Ein neues Boro-phosphat mit unverzweigten Vierer-Einfach Tetraederketten / Fe[B2P2O7(OH)5]: A New Borophosphate Containing Non-Branched Tetrahedral Vierer-Einfach Chains
  23. Polysulfonylamine, CIII [1] Ein Hydroxylamin mit bemerkenswert kurzer O-N-B Bindung: Kristall- und Molekülstruktur von MeO-N(SO2Me)2 / Polysulfonylamines, C III [1] A Hydroxylamine with a Remarkably Short O-N Bond: Crystal and Molecular Structure of MeO-N(SO2Me)2
  24. 3,10,17,24-Tetra(1-methylethyl)-[29H,31H-tetrapyrido[2,3-b:2′,3′-g:2″-3″-I:2‴,3‴ -q]porphyrazinato-(2-)N29,N30,N31,N32]-nickel- [Eu(fod)3]4- Ein lösliches Pyridoporphyrazin / 3,10,17,24-Tetra(1-methylethyl)- [29H,31H-tetrapyrido[2,3-b:2′,3′-g:2″-3″-I:2‴,3‴-q]porphyrazinato-(2-)N29,N30,N31,N32]-nickel-[Eu(fod)3]4 - A Soluble Pyridoporphyrazine
https://doi.org/10.1515/znb-1998-5-618
Keywords for this article
Geminal Bisonium Salts; SN-Reactions; Electrostatic Effects; Synthesis; X -Ray Data

Articles in the same Issue

  1. Darstellung und Strukturbeschreibung von NaCa3 Mn(V2O7)(V3O10) / Preparation and Structure of NaCa3Mn(V2O7)(V3O10)
  2. Ba4Mn2Ag2O(As04)4 , ein Barium-Mangan-Oxid-Arsenat mit nichtlinearen O-Ag-O-Hanteln / Ba4Mn2Ag2O(AsO4)4, a Barium Manganese Oxide-Arsenate Showing Nonlinear O-Ag-O Dumbbells
  3. Indium partiell in tetraedrischer Sauerstoffkoordination in BaIn2Zn3O7. Eine Betrachtung zum Ba2Ln2Zn8O13/BaLnAlZn3O7 -Typ / Partial Tetrahedral Oxygen Coordination of Indium in BaIn2Zn3O7. A Consideration of the Ba2Ln2Zn8O13/BaLnAlZn3O7 Type
  4. Zur Kenntnis eines Vanadyl-Oxocuprat-Phosphats CaCu(VO)(PO4)2 mit Cu2+ auf Positionen der VO2+-Ionen und einer kupferreicheren Phase CaCu1,13(VO)0,87(PO4)2 / On an Vanadyl Oxocuprate Phosphate CaCu(VO)(PO4)2 Containing Cu2+ at Positions of VO2+ Ions and a Copper Rich Phase CaCu1.13(VO)0.87(PO4)2
  5. Verknüpfung von (TeO6)6- und (TeO6)3(NiO6)3-Sechsringen durch TeNiO9-Oktaederdoppel in Pb3Ni4,5Te2,5O15 / Connection of (TeO6)6 and (TeO6)3(NiO6)3 Hexagons by TeNiO9 Octahedra Double in Pb3Ni4,5Te2,5O15
  6. Preparation and X-Ray Structure of 3,5-Dimethyl-1,4-dichloro-1,2,6- thiadiazine-1-oxide
  7. Pentafluoro[(4-methyl-1,4-bisazoniacy clohex-1 -yl)methy 1] germanate Hydrate: Synthesis and Crystal Structure of a Zwitterionic λ6Ge-Germanate with a GeF5C Framework
  8. Mesitylene Osmium(II) Complexes Containing the Functional Phosphane tBuP(CH2CO2Me)2 and Anionic Species Derived Thereof as Bi- and Tridentate Ligands
  9. Benzylgallium-Verbindungen. Die Kristallstrukturen von [Mg3Br2,4Cl1,6(OEt2)6][Ga(CH2Ph)4]2 · 0,5 Toluol und [(3,5-Me2C6H3CH2)2GaBr]2 / Benzylgallium Compounds. The Crystal Structures of [Mg3Br2,4Cl1,6(OEt2)6][Ga(CH2Ph)4]2 · 0.5 Toluene and [(3,5-Me2C6H3CH2)2GaBr]2
  10. Die Kristallstruktur von [Me3PN(H)PMe3]4l28, einem Polyiodid mit I3--, l82-- und I144--Ionen Crystal / Structure of [Me3PN(H)PMe3]4I28, a Polyiodide with I3-, I82- , and I 144- Ions
  11. In situ Neutron Diffraction on DxNb2O5
  12. The First Hydrogen Containing (Polyfluorocycloalken-l-yl)xenon(II) Salts
  13. Kristallstruktur von 1,1'-Dimethyl-4,4'-bipyridinium-octachlorodiantimonat(III) / Crystal Structure of 1,1'-Dimethyl-4,4'-bipyridinium-octachlorodiantimonate(III)
  14. Kristallstruktur des Doppelkomplexsalzes trans-(py2CH2)[Pt(OH)2(ox)2]transs-(py2CH2)[Pt(OH)(ox)2(H2O)]2·4H2O / Crystal Structure of the Double Complex Salt trans-(py2CH2)[Pt(OH)2(ox)2](H2O)]2·4H2O
  15. Tetrakis(sulfurdiimido)silane, -germane and -stannane
  16. Synthese und Charakterisierung von kronenetherstabilisierten Platin(IV)- Komplexen mit Aminosäureliganden / Synthesis and Characterization of Amino Acid Complexes of Platinum(IV) Stabilized by Crown Ethers
  17. Hydrido(acylphenolato)cobaIt(III)-Verbindungen mit Trimethylphosphan-Liganden / Hydrido(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands
  18. Onio-assistierte SN2-Reaktionen: Allgemeiner Zugang zu symmetrischen und unsymmetrischen geminal bisoniosubstituierten Methanderivaten / Onio-Assisted SN2-Reactions: General Access to Symmetrical and Unsymmetrical Geminally Bisonio Substituted Methane Derivatives
  19. Anodic Methoxylation of Isatin
  20. Neuartige Synthese und Molekülstruktur von Benzylkalium (thf) [KCH2C6H5]2 / Novel Synthesis and Molecular Structure of Benzyl Potassium (thf)[KCH2C6H5]2
  21. Weitere Verbindungen zum Ba6Nd2Al4O15-Typ: Ba4Nd4Zn3PtO15 und Ba4Eu4Zn3PtO15 / Further Compounds of the Ba6Nd2Al4O15 Type: Ba4Nd4Zn3PtO15 and Ba4Eu4Zn3PtO15
  22. Fe[B2P2O7(OH)5]: Ein neues Boro-phosphat mit unverzweigten Vierer-Einfach Tetraederketten / Fe[B2P2O7(OH)5]: A New Borophosphate Containing Non-Branched Tetrahedral Vierer-Einfach Chains
  23. Polysulfonylamine, CIII [1] Ein Hydroxylamin mit bemerkenswert kurzer O-N-B Bindung: Kristall- und Molekülstruktur von MeO-N(SO2Me)2 / Polysulfonylamines, C III [1] A Hydroxylamine with a Remarkably Short O-N Bond: Crystal and Molecular Structure of MeO-N(SO2Me)2
  24. 3,10,17,24-Tetra(1-methylethyl)-[29H,31H-tetrapyrido[2,3-b:2′,3′-g:2″-3″-I:2‴,3‴ -q]porphyrazinato-(2-)N29,N30,N31,N32]-nickel- [Eu(fod)3]4- Ein lösliches Pyridoporphyrazin / 3,10,17,24-Tetra(1-methylethyl)- [29H,31H-tetrapyrido[2,3-b:2′,3′-g:2″-3″-I:2‴,3‴-q]porphyrazinato-(2-)N29,N30,N31,N32]-nickel-[Eu(fod)3]4 - A Soluble Pyridoporphyrazine
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 16.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/znb-1998-5-618/html
Scroll to top button