Chapter 10. Novel Pentacoordinate Siliconium Complexes Stabilized by Oxygen and Nitrogen Donors: Highly Sensitive and Unusual Equilibrium between Ionic Penta- and Neutral Hexacoordinate Compounds

  1. Prof. Dr. Norbert Auner2 and
  2. Prof. Dr. Johann Weis3
  1. Daniel Kost,
  2. Vijeyakumar Kingston and
  3. Inna Kalikhman

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch10

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Kost, D., Kingston, V. and Kalikhman, I. (2003) Novel Pentacoordinate Siliconium Complexes Stabilized by Oxygen and Nitrogen Donors: Highly Sensitive and Unusual Equilibrium between Ionic Penta- and Neutral Hexacoordinate Compounds, in Organosilicon Chemistry V: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619924.ch10

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. Department of Chemistry, Ben-Gurion University of the Negev Beer-Sheva 84105, Israel Tel.: +972 8 646 1192 — Fax: +972 8 647 2943

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:

  • onic dissociation;
  • equilibrium reaction;
  • siliconium compounds;
  • neutral hexacoordinate complexes;
  • negative entropy

Summary

The first ionic dissociation of the Si–Cl bond in neutral hexacoordinate silicon complexes is reported. An equilibrium reaction between the ionic siliconium chloride and its neutral precursor (dissociation-recombination) is observed. The population ratio can be controlled by temperature or by replacement of the chloro ligand by a triflate group. The reaction enthalpy and entropy of the dissociation are both negative, suggesting that solvent organization facilitates dissociation at low temperature.