Chapter 39. Cyclic Silylhydrazines — Synthesis, Isomerizations, and Quantum Chemical Calculations

  1. Prof. Dr. Norbert Auner3 and
  2. Prof. Dr. Johann Weis4
  1. Uwe Klingebiel1 and
  2. Stefan Schmatz2

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch39

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Klingebiel, U. and Schmatz, S. (2003) Cyclic Silylhydrazines — Synthesis, Isomerizations, 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.ch39

Editor Information

  1. 3

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

  2. 4

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

Author Information

  1. 1

    Institut für Anorganische Chemie, Georg-August-Universität Tammannstraße 4, D-37077 Göttingen, Germany Tel.:+49 551 393052—–Fax:+49 551 393373

  2. 2

    Institut für Physikalische Chemie, Georg-August-Universität Tammannstraße 6, D-37077 Göttingen, Germany

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:

  • silylhydrazines;
  • rings;
  • isomerizations;
  • expansions;
  • transition states;
  • density functional theory

Summary

The synthesis and isomerization reactions of acyclic and cyclic silylhydrazines and silylparazolones are described. Topics of the discussion are: 1) the formation of the Si-form of silylpyrazolones; 2) the “side on” and “end on” coordination of lithium in silylhydrazides; 3) the expansion of the three-membered Si(SiN2) ring to the four-membered (SiN)2 ring by lithiation of the (SiN)2 ring and by thermal silyl group insertion into the N-N bond; 4) the expansion of a three-membered (SiN2) ring to a five-membered (CSi2N2) ring by insertion of SiCH2 into the Si-N bond; 5) the formation of isomeric four- and six-membered silylhydrazine rings; 6) the expansion of a five-membered (N2Si2N)N ring to the isomeric six-membered (SiNN)2 ring. The mechanisms of the isomerization are elucidated by quantum chemical calculations, and the molecular structures are verified by crystal structure determinations.