Chapter 40. Silylhydroxylamines — Synthesis, Isomerisation, and Quantum Chemical Calculations

  1. Prof. Dr. Norbert Auner2 and
  2. Prof. Dr. Johann Weis3
  1. Christina Ebker,
  2. Friedhelm Diedrich,
  3. Stefan Schmatz and
  4. Uwe Klingebiel

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch40

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Ebker, C., Diedrich, F., Schmatz, S. and Klingebiel, U. (2008) Silylhydroxylamines — Synthesis, Isomerisation, and Quantum Chemical Calculations, in Organosilicon Chemistry V: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619924.ch40

Editor Information

  1. 2

    Department of Inorganic Chemistry, University of Frankfurt, Marie-Curie-Straße 11, 60439 Frankfurt am Main, Germany

  2. 3

    Consortium of Electrochemical Industry GmbH, Zielstattstraße 20, 81379 Munich, Germany

Author Information

  1. Institute of Inorganic Chemistry, Georg August-University Göttingen Tammannstr. 4, D-37073 Göttingen, Germany Tel: +49 551 39 3052 — Fax: +49 551 39 3373

Publication History

  1. Published Online: 5 MAY 2008
  2. Published Print: 26 SEP 2003

ISBN Information

Print ISBN: 9783527306701

Online ISBN: 9783527619924

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Keywords:

  • silylhydroxylamines;
  • rearrangement;
  • calculations

Summary

Silylhydroxylamines were able to undergo anionic, neutral and thermal rearrangements. Lithium derivatives of silylhydroxylamines were formed in the reaction of N,O–bis(silyl)hydroxylamines with butyllithium and crystallized as 0–lithium-N,N-bis(silyl)hydroxylamides under silyl group migration from the O-atom to N-atom. Stable O,O'-bis(hydroxylamino)silanes have been isolated and characterized in a two-phase reaction. In the N,O-bis(fert-butyl-dimethylsilyl)-N-trimethyl-stannyl-hydroxylamine a 1,2-anionic stannyl group migration from oxygen to nitrogen and a silyl group migration from nitrogen to the oxygen via a dyotropic transition state was proved for the first time. Reactions, crystal structures, rearrangements and quantum chemical calculations are presented.