Chapter 24. N, O-Dimethyl-N-Silylhydroxylamine, a Compound with Steeply Pyramidal Nitrogen Coordination

  1. Prof. Norbert Auner3 and
  2. Prof. Johann Weis4
  1. Norbert W. Mitzel1 and
  2. Heinz Oberhammer2

Published Online: 28 APR 2008

DOI: 10.1002/9783527619917.ch24

Organosilicon Chemistry IV: From Molecules to Materials

Organosilicon Chemistry IV: From Molecules to Materials

How to Cite

Mitzel, N. W. and Oberhammer, H. (2000) N, O-Dimethyl-N-Silylhydroxylamine, a Compound with Steeply Pyramidal Nitrogen Coordination, in Organosilicon Chemistry IV: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619917.ch24

Editor Information

  1. 3

    Inst. für Anorganische Chemie, der Universität Frankfurt, Marie-Curie-Strasse 11, D-60439 Frankfurt am Main, Germany, Phone: 0 69/7 98-29180, -29591, Fax: 069/798-29188

  2. 4

    Wacker-Chemie GmbH, Geschäftsbereich S, Werk Burghausen, Johannes-Hess-Strasse 24, D-84489 Burghausen, Germany

Author Information

  1. 1

    Anorganisch-chemisches Institut der Technische Universität München Lichtenbergstr. 4, D-85747 Garching, Germany Tel. Int. code + (89)289 13066 — Fax. Int. code + (89) 289 13125

  2. 2

    Institut für Physikalische und Theoretische Chemie der Universität Tübingen Auf der Morgenstelle 8, D-72076 Tübingen, Germany

Publication History

  1. Published Online: 28 APR 2008
  2. Published Print: 17 JAN 2000

ISBN Information

Print ISBN: 9783527298549

Online ISBN: 9783527619917

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Keywords:

  • silylamines;
  • hydroxylamines;
  • gas-phase electron-diffraction;
  • ab initio calculations

Summary

N, O-Dimethyl-N-silylhydroxylamine, H3SiMeNOMe, has been prepared by reaction of HMeNOMe with H3SiBr and 2, 6-lutidine as an auxiliary base. The solution NMR data indicate aggregation of the compound. H3SiMeNOMe decomposes at ambient temperature and formation of methylnitrene is probably a first step in the mechanism. The energy of H3SiMeNOMe relative to its potential rearrangement isomer MeHN-H2Si-OMe has been estimated by ab initio calculations to be 289 kJ mol-1. The molecular structure of H3SiMeNOMe has been determined by gas-phase electron diffraction and by ab initio calculations. H3SiMeNOMe possesses a steeply pyramidal nitrogen atom. Hence it is the first silylamine reported with a typically pyramidal nitrogen coordination for electronic reasons. Results of an NBO analysis are discussed to rationalize the bonding situation.