Chapter 25. Strong β-Donor–Acceptor Bonds in Hydroxylaminosilanes

  1. Prof. Norbert Auner2 and
  2. Prof. Johann Weis3
  1. Norbert W. Mitzel and
  2. Udo Losehand

Published Online: 28 APR 2008

DOI: 10.1002/9783527619917.ch25

Organosilicon Chemistry IV: From Molecules to Materials

Organosilicon Chemistry IV: From Molecules to Materials

How to Cite

Mitzel, N. W. and Losehand, U. (2000) Strong β-Donor–Acceptor Bonds in Hydroxylaminosilanes, in Organosilicon Chemistry IV: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619917.ch25

Editor Information

  1. 2

    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. 3

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

Author Information

  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

Publication History

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

ISBN Information

Print ISBN: 9783527298549

Online ISBN: 9783527619917



  • donor bonds;
  • gas-phase electron-diffraction;
  • crystal structure;
  • ab initio calculations;
  • hydroxylamines


ClHzSiONMe2 and its ethyl analogue have been prepared and studied by a variety of spectroscopic methods. ClH2SiONMe2 adopts an extremely small Si-O-N angle in the solid state corresponding to an unusually strong secondary bond between Si and N atoms (β-donor bond). In the gas phase (electron diffraction) two conformers are present: anti, with a strong β-donor bond (weaker than in the crystal), and gauche, with a comparatively weak β-donor bond. The gaslsolid differences can be explained in terms of increasing dipole moment with stronger β-donor bonds, the differences between the two conformers can be rationalized in terms of negative hyperconjugation of the type p(lp-N) [RIGHTWARDS ARROW] s *(Si-X), whereby the nature of X and its orientation relative to the Si-O-N plane are of major importance. Electrostatic interaction between Si and N atoms are not suitable to rationalize the experimental facts. The behavior in solution is still not well understood.